SYNTHESIS AND STRUCTURE DETERMINATION OF K2Ti6O13 NANOWIRES

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原料药DMF编写要点-中英对照

原料药DMF使用说明：1、本大纲是为了帮助我公司客户把握DMF的整体内容而准备的，由于DMF内容繁多，从整体上了解内容框架和组成部分，对于理解FDA对DMF的要求和意图非常有必要；2、根据FDA的要求，凡是本大纲提到的内容，原料药制造商均应该提供。

因此，客户务必依照规定提供尽可能详细的内容。

3、本大纲的内容和相关要求能够确保客户目前的运作达到FDA的cGMP标准，因此，准备DMF的过程，也使客户按照FDA的要求进行整改和提高的过程，这些都为FDA未来的现场检查打下良好基础；4、凡是本大纲中提到的非技术性具体内容要求，请参照本公司专有的与此大纲配套的相关DFM指导性文件，包括《FDA药物主文件指南》、《关于在药品递交中递交的有关原料药生产的支持文件的指南》、《药物申办中质量管理方面通用技术文件格式与内容要求》；5、凡是本大纲中提到的技术性具体内容要求，如杂质、稳定性、验证等具体技术要求，请参照本公司专有的FDA相关技术标准文件，包括《原料药认证指南》、《制剂认证指南》、《化学药物稳定性指南》、《化学药物杂质指南》、《化学药物化验与合格参数指南》、《化学药物验证指南》等；《合成原料药DMF起草大纲》一、公司和生产场地的基本描述1、第一类的DMF文件建议由位于美国之外的人提供，以帮助FDA对他们的生产设施进行现场检查。

DMF文件应描述生产场地、设备能力、生产流程图等。

A Type I DMF is recommended for a person outside of the United States to assist FDA in conducting on site inspections of their manufacturing facilities. The DMF should describe the manufacturing site, equipment capabilities, and operational layout.2、第一类的DMF文件对美国国内设施通常不需要，除非该设施没有登记并定期接受检查。

化学课程英文名称对照表

化学课程英文名称对照表磁共振实验Magnetic Resonance Experiment磁共振在化学和生命科学中应用Application of Magnetic Resonance inChemistry and Life Science核磁共振波谱学Nuclear Magnetic Resonance Spectroscopy核磁共振新技术及其应用Movdern Nuclear Magnetic Resonance Spectroscopy and its Application角动量理论与原子结构Angular Momentum Theory & Atomic Structure聚合物改性原理与流变学The Principle of Modification and Theology of Polymer量子化学Quantum Chemistry量子化学计算方法Quantum Chemistry B谱学原理和应用Principles of Spectroscopes and TheirChemical Applications群论及其在量子化学中的应用Group Theory and Its Application to QuantumChemistry材料化学导论Introduction of Material Chemistry分析化学Analytical Chemistry高等无机化学Advanced Inorganic Chemistry高等有机化学Advanced Organic Chemistry结构化学Structural Chemistry结构化学Structural Chemistry无机化学Inorganic Chemistry无机化学Inorganic Chemistry无机及分析化学Inorganic and Analytic Chemistry无机及分析化学Inorganic and Analytic Chemistry物理化学Physical Chemistry物理化学Physical Chemistry物理化学Physical Chemistry物理化学Physical Chemistry物理化学Physical Chemistry仪器分析Instrumental Analysis仪器分析Instrumental Analysis仪器分析Instrumental Analysis有机化学Organic Chemistry有机化学Organic Chemistry有机化学Organic Chemistry有机化学Organic Chemistry量子无机化学Quantum Inorganic Chemistry量子有机化学Quantum Organic Chemistry植物生长与发育的化学调整Chemical Adjustment of Plant's Growth分析化学Analysis Chemistry分析化学及实验Analytical Chemistry and Experiment分析化学实验Experiment of Analytical Chemistry计算机基础(C语言) Computer Basis C Language普通物理学General Physics无机化学实验Experiment in Inorganic Chemistry无机化学实验Experiment in Inorganic Chemistry无机化学实验Experiment in Inorganic Chemistry无机化学实验Experiment in inorganic Chemistry物理化学实验Experiment of Physical Chemistry物理化学实验Experiment of Physical Chemistry物理化学实验Experiment of Physical Chemistry物理化学实验Experiment of Physical Chemistry仪器分析实验Experiments of Instrument Analysis有机化学实验Organic Chemistry Experiment有机化学实验Organic Chemistry Experiment有机过渡金属化学Organotransition Metal ChemistryX射线晶体结构分析Crystal Structure Analysis by X-ray电分析化学实验Experiment in Electroanalytical Chemistry分子发光分析Molecular Luminescence Analysis分子发光分析进展Advances in Molecular Luminescence Analysis 高分子材料化学Polymer Chemistry高分子材料研究方法Research Methods of Polymeric Materials高分子合成与分子设计Polymeric Synthesis and Molecular Design 高分子化学实验Experiment of Polymeric Chemistry高分子物理实验Experiment of Polymer Physics化学分离法Chemical Method of Separation化学计量学Chemometrics化学统计力学和应用Statistical Mechanics and Applications in Chemistry化学文献Chemical Document化学文献Scientific Literature in Chemistry化学文献Chemical Literature化学文献Chemical Literature Searching金属有机高聚物Metallic Organic Polymer近代电分析Electroanalytical Chemistry近代分离分析Analytical Separation and Chromatography近代光分析Modern Light Analysis配位化学* Coordination Chemistry配位化学选读Selective Topics on Modern Coordination Chemistry无机材料化学The Chemistry of Inorganic Materials无机材料实验Experiment in Inorganic Materials无机材料物理Polymeric Materials Physics无机合成与研究方法Synthesis and Research Methods for Inorganic Substance无机物研究法Research Methods of Inorganic Substance 无机元素化学Inorganic Elements Chemistry物化专门化实验Physical Chemistry Experiment物化专门化实验Physical Chemistry Experiment物化专门化实验Physical Chemistry Experiment物理有机化学Physical Organic Chemistry仪器分析选读Advanced Instrumentation in Chemistry有机分析Analysis and Structure Determination of Organic Compounds有机分析实验Organic Analytic Experiment有机合成Organic Synthesis有机合成化学Synthetic Organic Chemistry有机合成实验Organic Synthesis Experiment有机化学文献Document of Organic Chemistry专业英语(分析) Scientific English on Analytical Chemistry 专业英语(无机) Specialty English专业英语(有机) Subject English专业英语(物化) Chemistry English生物无机化学Bioinorganic Chemistry生物无机化学Bioinorganic Chemistry材料工程导论Introduction of Materials Engineering 环境分析化学Environmental Analytical Chemistry 界面化学Surface Chemistry应用电化学Applied Electronic chemistry荧光分析法Flueremetry普通化学General Chemistry普通化学实验General Chemistry Experiments。

花状二氧化铈的合成与表征

本科生毕业设计（论文）中文题目花状二氧化铈的合成与表征外文题目Synthesis and Characterization of FlowerlikeCeria学号1107130035姓名邹灵学院化学化工学院专业材料化学年级2011级指导老师钟声亮完成时间2015年4月江西师范大学教务处毕业论文声明本人郑重声明：1．此毕业论文是本人在指导教师指导下独立进行研究取得的成果。

除了特别加以标注地方外，本文不包含其他人或其它机构已经发表或撰写过的研究成果。

对本文研究做出重要贡献的个人与集体均已在文中作了明确标明。

本人完全意识到本声明的法律结果由本人承担。

2．本人完全了解学校、学院有关保留、使用学位论文的规定，同意学校与学院保留并向国家有关部门或机构送交此论文的复印件和电子版，允许此文被查阅和借阅。

本人授权江西师范大学政法学院可以将此文的全部或部分内容编入有关数据库进行检索，可以采用影印、缩印或扫描等复制手段保存和汇编本文。

3．若在江西师范大学政法学院毕业论文审查小组复审中，发现本文有抄袭，一切后果均由本人承担，与毕业论文指导老师无关。

学位论文作者（签名）：年月中文摘要二氧化铈是一种重要的稀土金属氧化物，在能源、材料、化工等领域有着重要的作用和广阔的前景。

由于花状二氧化铈特殊的形态和物理化学性质，研究花状二氧化铈的合成与表征对推广二氧化铈的应用有重要的意义。

在本文中，采取以六水合硝酸铈为原料，均苯四甲酸为配体，DMF（N,N-二甲基甲酰胺）为溶剂的溶剂热合成法，成功合成结构均匀且呈花状结构的铈的配位聚合物。

而且经过4h，700℃的煅烧以后得到的同样是三维层状结构的花状二氧化铈。

实验表明，反应温度与反应时间的变化可能会改变产物的形貌。

本文中的数据结果均是在10h，100℃反应条件下测定的。

关键词：二氧化铈；花状；溶剂热法。

AbstractCeria, as one of the most important rare metal oxide on the earth, There are broad prospects at Energy, Material and chemical industry. Researching the Synthesis and characterization of efflorescent ceria plays an important role at promoting its application, because of the special form and the physical and chemical properties.In the synthesis, the efflorescent ceria have been successfully synthetized by a simple method, which need Six hydrated cerium nitrate as raw material, 1,2,4,5-benzenetetracarboxylic acid (BTTA) as ligands,DMF(N,N-dimethylformamde) as solvent. And after calcination in air at 700 °C for 4 h, the same as flower shaped three-dimensional layered structure of cerium oxide is obtained. The experimental surface that the morphology of the product may turn different for the change of the reaction conditions.In this paper, the results of the data are in 10 h, 100 ℃under the reaction conditions of determination.Key words: ceria; efflorescent; solvent thermal method.目录毕业论文声明 (2)中文摘要 (3)Abstract (4)第一章绪论 (6)一、纳米材料概述 (6)二、二氧化铈简介 (6)三、合成方法简介 (8)四、二氧化铈的结构 (8)五、表征方法 (10)（一）扫描电子显微镜(SEM) (10)（二）X射线衍射分析（XRD） (10)（三）热重-差热分析（TG-DTA） (11)（四）红外光谱分析（IR） (11)五、论文的选题依据和主要内容 (11)第二章实验部分 (12)二、实验原料及实验设备 (12)（一）实验原料 (12)（二）实验设备 (12)二、实验步骤 (12)三、表征手段 (13)第三章结果与讨论 (14)一、扫描电镜分析 (14)二、红外光谱分析 (16)三、热重-差热分析 (16)第四章结论 (19)参考文献 (20)第一章绪论一、纳米材料概述纳米材料是三维空间中至少有一维尺寸在1-100nm之间的材料或由这种大小离子作为基本单元构成的材料，这种材料具有与众不同的性质。

水热溶剂热法——分子筛形貌(晶面)可控催化剂的制备

万颖，女，1975年出生于山西省。现为上海师范大学化学系教授。1992年考入华东理工大学化学系学习，2002年获得工学博士学位。2005年9月至 2007年6月在复旦大学进行博士后研究。她主要围绕杂化介孔材料的组装及其在绿色化学及污染治理过程中的催化应用开展基础科学研究。近年发表 SCI论文60余篇，论文被引用2000余次。出版专著1 部，参与撰写3部专著。2010年获得上海市优秀学科带头人和中国化学会青年化学奖。
作者：谢在库等出版社：中国石化出版社出版时间：2010年01月《新结构高性能多孔催化材料》是《国家重点基础研究发展计划》项目“新结构高性能多孔催化材料创制的基础研究”的系统总结。涉及多孔催化材料孔结构调变、催化功能化修饰、原位表征和理论模拟以及石油化工催化应用等内容，包括含骨架杂原子的亚纳米孔催化材料、多级复合孔催化材料、有机一无机杂化多孔催化材料、金属及氧化物修饰与组装的多孔催化材料、反应控制相转移及选择氧化多孔催化材料、催化材料原位动态谱学表征、催化新材料合成的分子设计与方法等方面的研究进展。
【书名】杂原子磷铝分子筛及应用【作者】张瑞珍【ISBN】9787122055088 【出版社】化学工业出版社【出版日期】2009-06-01
《有序介孔分子筛材料》是作者根据十几年来从事介孔分子筛材料研究的成果并结合国内外相关领域发展而撰写的一部学术专著。《有序介孔分子筛材料》以有序介孔分子筛材料的合成、结构和应用为主线，全面、系统地介绍了介孔分子筛材料合成原理、结构表征接术、形貌控制和功能化，并结合研究前沿展望了其发展趋势。书中着重从基础科学的角度理解介孔材料及其应用，目的是希望研究者，即使是初学者，阅读本书后能理解介孔分子筛中的化学原理，掌握其合成技巧，获得高质量的介孔材料并开发其应用。

有机／杂多酸-钆配合物的合成及电化学性质研究

有机／杂多酸-钆配合物的合成及电化学性质研究王小玉;李晨阳;尹佳成;蔡东明;丁海林;刘裕堃;王娟【摘要】以2，6-吡啶二羧酸和硅钨酸为配体合成了一种新型的稀土金属配合物，并对其进行了红外光谱、紫外光谱、荧光光谱、热重、电化学等表征。

结果表明，该配合物在196 nm 和253 nm 处具有较强的紫外吸收峰；在624 nm 处有一个很强的荧光发射峰；热稳定性较好；在－0．25～0．2 V（vs ．SCE）的电势范围内有一对氧化还原峰，具有良好的电化学活性。

%A novel rare earth metal complex was synthesized using 2,6-pyridinedicarboxylic acid and silico-tungstic acid as ligands,and the prepared complex was characterized by FTIR,UV,fluorescence,thermal gravi-metric and electrochemicalanalysis.Results showed that the complex had strong UV absorption peaks at 196 nm and 253 nm,strong fluorescence emission peak at 624 nm;the complex had good thermal stability and a pair of redox peak in potential range of -0.25~0.2 V(vs.SCE)which showed its good electrochemical activity.【期刊名称】《化学与生物工程》【年(卷),期】2015(000)011【总页数】3页(P28-30)【关键词】多金属氧酸盐;有机/杂多酸-钆配合物;合成;电化学性质【作者】王小玉;李晨阳;尹佳成;蔡东明;丁海林;刘裕堃;王娟【作者单位】江西省科学院应用化学研究所，江西南昌 330029;湖北大学化学化工学院，湖北武汉 430062;湖北大学化学化工学院，湖北武汉 430062;湖北大学化学化工学院，湖北武汉 430062;湖北大学化学化工学院，湖北武汉 430062;湖北大学化学化工学院，湖北武汉 430062;湖北大学化学化工学院，湖北武汉430062【正文语种】中文【中图分类】TQ0020世纪以来，对于稀土金属的研究越来越广泛，特别是在配位化学领域[1－3］。

MIL-100(Fe)

Synthesis and catalytic properties of MIL-100(Fe),an iron(III )carboxylate with large pores {Patricia Horcajada,a Suzy Surble ´,a Christian Serre,*a Do-Young Hong,b You-Kyong Seo,b Jong-San Chang,b Jean-Marc Grene `che,c Irene Margiolaki d and Ge ´rard Fe ´rey aReceived (in Cambridge,UK)21st March 2007,Accepted 1st May 2007First published as an Advance Article on the web 15th May 2007DOI:10.1039/b704325bThe large-pore iron(III )carboxylate MIL-100(Fe)with a zeotype architecture has been isolated under hydrothermal conditions,its structure solved from synchrotron X-ray powder diffraction data,while Friedel–Crafts benzylation catalytic tests indicate a high activity and selectivity for MIL-100(Fe).The recent interest in the synthesis of hybrid inorganic–organic solids gives a new dimension to the domain of porous compounds.1–4They offer significant new scientific and technolo-gical opportunities 5by combining attractive features of both inorganic and organic moieties and lead to many potential applications in gas storage,6,7catalysis,8,9insertion,10,11magnet-ism,12,13optical devices,14etc .Most of them are prepared using functionalized organic ligand (phosphonates,carboxylates,sulfo-nates...)and many elements in the Periodic Table have been incorporated in these new framework materials exhibiting novel structures not seen in zeolite chemistry.The introduction of 3d transition metals within the skeleton provides new electronic properties.Among them,iron is an environmentally benign and cheap component with non-toxicity and redox properties.However,to the best of our knowledge,while some MOF materials have been reported to date with iron(II )or iron(III ),15–20only two of them combine a permanent porosity and large pores.21,22We report here the successful synthesis and structure determination of MIL-100(Fe)(MIL:Materials of Institut Lavoisier),a new scarce example of an iron(III )carboxylate with a large accessible and permanent porosity.This solid was isolated as a polycrystalline powder from a reaction mixture of composition 1.0Fe 0:0.661,3,5-BTC :2.0HF :1.2HNO 3:280H 2O (1,3,5-BTC =benzene tricarboxylic or trimesic acid)that was held at 150u C in a Teflon-lined autoclave for 6days with a initial heating ramp of 12h and a final cooling ramp of 24h.The pH remains acidic (,1)throughout the synthesis.The light-orange solid product was recovered by filtration and washed with deionized water.A treatment in hotdeionised water (80u C)for 3h was applied to decrease the amount of residual trimesic acid (typically,1g of MIL-100(Fe)in 350ml of water)followed by drying at room temperature.A laboratory powder X-ray diffraction pattern showed that crystalline phase had been produced,isostructural with the chromium carboxylate MIL-100(Cr).23Elemental analysis indicated that the contents of Fe,F,C and H (obs:13.8%Fe,1.3%F,23.5%C)are in good agreement with the values based on the structure formula,Fe III 3O(H 2O)2F ?{C 6H 3(CO 2)3}2?n H 2O (n y 14.5)despite an excess of carbon content (calc.:14%Fe,1.8%F,21.0%C).It has not been possible to prepare sizeable crystals for single-crystal diffraction studies whatever the synthesis conditions.Thermal analysis (TGA2050TA apparatus,O 2flow,heating rate 3K min 21)shows three weight losses between 298and 873K.The first (y 40.1%)at 373K is attributed to the departure of the free water molecules inside the pores.The second at 473K (y 4.5%)comes from the water molecules which interact with the iron trimers.The final weight loss (y 35.3%)at 573K is related to the combustion of the trimesic acid.These latter two losses are,on the whole,in agreement with the theoretical values (calc:4.6and 35.2%).Note that the free water content deduced from the structure determination (y 29.5%)is slightly lower than the experimental value (TGA).This is due to the variable water content in MIL-100solids which vary considerably depending on the atmospheric conditions.The structure of title solid was solved from high-resolution synchrotron X-ray powder diffraction data using coordinates of MIL-100(Cr)as the starting model (ESI {).{The final Rietveld plot is shown in -100(Fe)is an iron(III )carboxylate built up from trimers of iron octahedra sharing a common vertex m 3-O.The trimers are then linked by the benzene-1,3,5-tricarboxylate moieties in such a way that this leads to the formation of hybrid supertetrahedra which further assemble into a zeolitic architecture of the MTN type (Fig.2).This delimits two types of mesoporouscages of free apertures of ca.25and 29A˚,accessible through microporous windows of ca. 5.5and 8.6A˚.Bond valence calculations indicate a trivalent state of iron.As is illustrated in Fig.3,the transmission Mo ¨ssbauer spectra recorded at 300and 77K consist of asymmetrical quadrupolar doublets with broadened and overlapped lines,in agreement with the large number of different environments of Fe atoms.24Whatever the fitting model,the isomer shift values (0.54and 0.42mm s 21at 300K and 77K,respectively)remain consistent with the presence of high spin state of Fe 3+ions located in octahedral units.Taking into account the crystallographic structure,one might describe the spectra by means of sevena Institut Lavoisier,UMR CNRS 8180,Universite ´de Versailles Saint-Quentin-en-Yvelines,45Avenue des Etats-Unis,78035,Versailles Ce ´dex,France.E-mail:serre@chimie.uvsq.fr;Fax:0033139254358;Tel:0033139254305;bCatalysis Centre for Molecular Engineering,Korea Research Institute of Chemical Technology (KRICT),Jang-dong 100,Yuseong-Gu,305-600,Daejon,South Korea cLaboratoire de Physique de L’Etat Condense ´,UMR CNRS 6087,Universite ´du Maine,72085,Le Mans Cedex 9,France dESRF,rue J.Horowitz,38043,Grenoble Cedex,France{Electronic supplementary information (ESI)available:Crystallographic details,TGA,adsorption,Mo ¨ssbauer and catalysis data.See DOI:10.1039/b704325bCOMMUNICATION /chemcomm |ChemComm2820|mun.,2007,2820–2822This journal is ßThe Royal Society of Chemistry 2007D o w n l o a d e d o n 20 S e p t e m b e r 2011P u b l i s h e d o n 15 M a y 2007 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/B 704325Bdifferent quadrupolar components:different solutions can be found without any clear and sound interpretation.On the contrary,assuming that three main types of Fe octahedral units can be distinguished according to their nearest chemical environ-ments,this gives rise to a reasonable fitting model involving three quadrupolar components,as shown in Fig. 3.This could be explained by the presence of different fluorine environments for the iron atoms within the structure.It has been proved previously with the isostructural solid MIL-100(Cr)that the distribution offluorine atoms bound to chromium atoms from the trimers,was at the origin of the three types of environments for the metal sites as evidenced by CO adsorption experiments.25Thus,as MIL-100(Fe)possesses the same fluorine composition as MIL-100(Cr),i.e.one fluorine atom per trimer,a similar environment is expected.The different values of isomer shift confirm this hypothesis with some Fe ions mainly surrounded by O while the environment of others (with higher isomer shift)also contain F ions.The values of quadrupolar splitting (0.30,0.52and 0.90mm s 21)are consistent with different degrees of distortions and the highest distorted octahedral unit contains F anions.Finally,the significant increase of the absorption spectral area when decreasing the temperature should be noted.This is due to a large increase of the Debye–Waller factor,resulting from the strengthening of the structure,particularly due to its hybrid character which is temperature sensitive.The permanent porosity of the new solid was measured by N 2adsorption experiments performed in liquid -100(Fe)revealed an adsorption isotherm characteristic of micro-porous solids (Fig.4).However,due to the presence of two types of microporous windows and mesoporous cages with different sizes,two secondary uptakes at ca.P /P 0=0.06and 0.12can be distinguished from the isotherm,in agreement with our previous results with MIL-100(Cr).23The corresponding Langmuir surface area is estimated to be .2800(100)m 2g 21.This value is,on the whole,in agreement with that of the isostructural solid MIL-100(Cr)(S =3100m 2g 21).The thermal stability ofMIL-100(Fe)Fig.1Final Rietveld refinement plot for Fe III 3O(H 2O)2F ?{C 6H 3(CO 2)3}2?n H 2O (MIL-100(Fe))in the space group Fd 3¯m .Observed,calculated and difference profiles are plotted on the same scale.Inset is an expanded region of a small part of thedata.Fig.2Structure of MIL-100(Fe).(A)A trimer of iron octahedra and trimesic acid.(B)Schematic view of one unit cell of MIL-100(Fe).(C)the two types of cages in polyhedral mode.(D)Pentagonal and hexagonal windows in balls and sticks (Fe:grey;O:red;C:black).Fig.3Transmission Mo ¨ssbauer spectra of MIL-100(Fe)recorded at 300and 77K.Fig.4N 2adsorption isotherm of MIL-100(Fe)at 77K (P 0=1atm).This journal is ßThe Royal Society of Chemistry 2007mun.,2007,2820–2822|2821D o w n l o a d e d o n 20 S e p t e m b e r 2011P u b l i s h e d o n 15 M a y 2007 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/B 704325Bhas been studied by X-ray thermodiffractometry and reveals that this solid is stable up to 270u C.The use of heterogeneous catalysts in the liquid phase is highly desirable for Friedel–Crafts type reactions 27because the use of conventional homogeneous catalysts for these reactions leads to several problems,such as difficulty in separation and recovery,disposal of spent catalyst and corrosion.In the light of the importance of heterogenous catalysis,we have performed Friedel–Crafts benzylation to confirm the suitability of iron-containing MIL-100as a new porous catalyst (see ESI {).Fig.5shows the conversion of benzyl chloride in the liquid phase benzylation of benzene by benzyl chloride (BZC)to diphenylmethane (DPM)at 70u C over MIL-100(Fe),MIL-100(Cr)and zeolite catalysts for comparison.We find that MIL-100(Fe)gives high activity and selectivity,showing 100%BZC conversion [X (BZC)]with nearly 100%DPM selectivity [S (DPM)]being quickly attained after a short induction period (5min).By contrast,MIL-100(Cr)was poorly active for the reaction,i.e.,42%X (BZC)after 30h.Solid acid catalysts such as HBEA and HY zeolites were not so active under the same reaction conditions:43.4%X (BZC)with 97.6%S (DPM)for HBEA and 54.0%X (BZC)with 95.8%S (DPM)for HY after 5h.These results clearly indicate that iron species in MIL-100(Fe)play a role as catalytically active sites in Friedel–Crafts alkylation.The observed high benzylation activity of MIL-100(Fe)might be attributed to the redox property of trivalent iron species (Fe 3++e 2«Fe 2+)to play a significant role in activating both the reactants,consistent with results observed in iron-containing solid catalysts.26–28The origin of the induction period in the benzylation is generally ascribed to the inhibition effect by moisture present in the catalyst and/or in the reaction mixture 26or the diffusion limitation of reactant molecules into the active site in the pore.In summary,we report the synthesis and characterisation of a new example of a large-pore iron(III )carboxylate under hydro-thermal conditions.First catalytic experiments suggest that iron(III )species metal sites are particularly interesting in catalysis and might lead to new applications.We are currently surveying phases produced from other iron(III )carboxylate systems.This work was supported by CNRS,the EU funding via FP6-Specific Targeted Research Project DeSANNS (SES6-020133),theKorea Ministry of Commerce,Industry and Energy through the Research Center for Nanocatalysis (TS066-26)and the Institutional Research Program (KK-0703-E0).The KRICT s authors thank Dr S.H.Jhung and Dr Y.K.Hwang for helpful discussion.We thank ESRF for provision of synchrotron beam time.Notes and references{Coordinates of MIL-100(Fe)have been deposited with the CCDC data bank,deposition number CCDC 640536.For crystallographic data in CIF or other electronic format see DOI:10.1039/b704325b1G.Fe ´rey,C.Mellot-Draznieks,C.Serre and lange,Acc.Chem.Res ,2005,38,217.2H.Li,M.Eddaoudi,M.O’Keeffe and O.M.Yaghi,Nature ,1999,402,276.3S.Kitagawa and K.Uemura,Chem.Soc.Rev.,2005,34,109.4Y.Liu,V.C.Kravtsov,rsena and M.Eddaoudi,mun.,2006,1488.5U.Mueller,M.Schubert,F.Teich,H.Puetter,K.Schierle-Arndt and J.Pastre,J.Mater.Chem.,2006,16,626.6G.Fe ´rey,troche, C.Serre,T.Loiseau, lange and A.Percheron-Guegan,mun.,2003,2276.7A.G.Wong-Foy,A.J.Matzger and O.M.Yaghi,J.Am.Chem.Soc.,2006,128,3494.8J.S.Seo,D.Whang,H.Lee,S.I.Jun,J.Oh,Y.J.Jeon and K.Kim,Nature ,2000,404,982.9R.-Q.Zou,H.Sakurai and Q.Xu,Angew.Chem.,Int.Ed.,2006,45,2542.10G.Fe ´rey, C.Mellot-Draznieks, C.Serre, lange,J.Dutour,S.Surble ´and I.Margiolaki,Science ,2005,309,2040.11S.Hermes,M.K.Schro ¨ter,R.Schmid,L.Khodeir,M.Muhler,A.Tissler,R.W.Fischer and R.A.Fischer,Angew.Chem.,Int.Ed.,2005,44,6237.12S.Konar,P.S.Mukherjee, E.Zangrando, F.Lloret andN.R.Chaudhuri,Angew.Chem.,Int.Ed.,2002,41,1561.13G.Guillou,C.Livage,M.Drillon and G.Fe ´rey,Angew.Chem.,Int.Ed.,2003,115,5472.14F.Pelle ´,S.Surble ´,C.Serre,lange and G.Fe ´rey,J.Lumin.,2007,122–123,492.15M.Sanselme,J.M.Grene `che,M.Riou-Cavellec and G.Fe ´rey,mun.,2002,2172.16C.Serre,lange,S.Surble´and G.Fe ´rey,Angew.Chem.,Int.Ed.,2004,43,6286.17W.Schmitt,J.P.Hill,M.P.Juanico,A.Caneschi,F.Costantino,C.E.Anson and A.K.Powell,Angew.Chem.,Int.Ed.,2005,44,4187.18T.R.Whitfield,X.Wang,L.Liu and A.J.Jacobson,Solid State Sci.,2005,7,1096.19S.Surble ´,C.Serre,C.Mellot-Draznieks,lange and G.Fe ´rey,mun.,2006,284.20C.Serre,lange,S.Surble ´,J.M.Grene `che and G.Fe ´rey,Chem.Mater.,2004,16,2706.21A.C.Sudik,A.P.Co ˆte ´,A.G.Wong-Foy,M.O’Keefe and O.M.Yaghi,Angew.Chem.,Int.Ed.,2005,118,2590.22J.Jia,X.Lin,C.Wilson,A.J.Blake,N.R.Champness,P.Hubberstey,G.Walker,E.J.Cussena and M.Schro ¨der,mun.,2007,840.23G.Fe ´rey, C.Serre, C.Mellot-Draznieks, lange,S.Surble ´,J.Dutour and I.Margiolaki,Angew.Chem.,Int.Ed.,2004,43,6296.24J.Teillet and F.Varret,in ‘MOSFIT program’.25A.Vimont,J.-M.Goupil,valley,M.Daturi,S.Surble ´,C.Serre,lange,G.Fe ´rey and N.Audebrand,J.Am.Chem.Soc.,2006,128,3218.26V.R.Choudhary and S.K.Jana,Appl.Catal.,A ,2004,224,51.27T.Cseri,S.Bekassy,S.Rizner and F.Figueras,J.Mol.Catal.A:Chem.,1995,98,101.28M.S.Hamdy,G.Mul,J.C.Jansen,A.Ebaid,Z.Shan,A.R.Overweg and T.Maschmeyer,Catal.Today ,2005,100,255.Fig.5Benzyl chloride conversion in the Friedel–Crafts benzylation of benzene over different catalysts.Reaction conditions :70u C,7.8ml benzene,benzene/benzyl chloride =10(molar ratio),0.1g catalyst.2822|mun.,2007,2820–2822This journal is ßThe Royal Society of Chemistry 2007D o w n l o a d e d o n 20 S e p t e m b e r 2011P u b l i s h e d o n 15 M a y 2007 o n h t t p ://p u b s .r s c .o r g | d o i :10.1039/B 704325B。

对苯二甲酸锌

对苯⼆甲酸锌Hydrothermal Synthesis and Crystal Structure of a Novel 2-Fold Interpenetrated Framework Based on Tetranuclear Homometallic ClusterRong-Yi Huang ?Xue-Jun Kong ?Guang-Xiang LiuReceived:15December 2007/Accepted:11January 2008/Published online:5March 2008óSpringer Science+Business Media,LLC 2008Abstract A novel 2-fold parallel interpenetrated polymer,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1)(pheno =phenan-threne-9,10-dione;p -BDC =1,4-benzenedicarboxylate)was prepared by hydrothermal synthesis and characterized by IRspectra,elemental analysis and single crystal X-ray /doc/c97a12ccf61fb7360b4c65f3.html plex1crystallizes in the orthorhombic space group Pbca and affords a three-dimensional (3D)six-connected a -Ponetwork.Keywords Carboxylate ligand áHomometallic complex áa -Po1IntroductionIn the last decade,the construction by design of metal-organic frameworks (MOFs)using various secondary building units (SBUs)connected through coordination bonds,supramolecular contacts (e.g.,hydrogen bonding,p áááp stacking,etc.),or their combination has been an increasingly active research area [1].The design and controlled assembly of coordination polymers based on nano-sized MO(OH)clusters and multi-functional car-boxylates have been extensively developed for their crystallographic and potential applications in catalysis,nonlinear optics,ion exchange,gas storage,magnetism and molecular recognition [2].In most cases,multinu-clear metal cluster SBUs can direct the formation of novel geometry and topology of molecular architectureand help to retain the rigidity of the networks [3].A number of carboxylate-bridged metal clusters have been utilized to build extended coordination frameworks.Among these compounds,frameworks from multinuclear zinc cluster SBUs,including dinuclear (Zn 2)[4],trinu-clear (Zn 3)[5],tetranuclear (Zn 4)[6],pentanuclear (Zn 5)[7],hexanuclear (Zn 6)[8],heptanuclear (Zn 7) [9],and octanuclear (Zn 8)[10]clusters have attracted great interest and have been investigated extensively.Addi-tionally,a series of systematic studies on this subject has demonstrated that an interpenetrated array cannot prevent porosity,but enhances the porous functionalities of the supramolecular frameworks [11].More importantly,the research upsurge in interpenetration structures was pro-moted by the fact that interpenetrated nets have been considered as potential super-hard materials [12]and possess peculiar optical and electrical properties [13].Herein we present the synthesis,structure,and spectral properties of a new coordination polymer based on tetranuclear homometallic cluster,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1).2Experimental2.1Materials and MeasurementsAll commercially available chemicals are reagent grade and used as received without further puri?cation.Sol-vents were puri?ed by standard methods prior to use.Elemental analysis for C,H and N were carried with a Perkin-Elmer 240C Elemental Analyzer at the Analysis Center of Nanjing University.Infrared spectra were obtained with a Bruker FS66V FT IR Spectrophotometer as a KBr pellet.R.-Y.Huang áX.-J.Kong áG.-X.Liu (&)Anhui Key Laboratory of Functional Coordination Compounds,College of Chemistry and Chemical Engineering,Anqing Normal University,Anqing 246003,P.R.China e-mail:liugx@/doc/c97a12ccf61fb7360b4c65f3.htmlJ Inorg Organomet Polym (2008)18:304–308DOI 10.1007/s10904-008-9199-72.2Preparation of Zn2(OH)(pheno)(p-BDC)1.5áH2O(1)A mixture containing Zn(NO3)2á6H2O(0.20mmol), p-1,4-benzenedicarboxylic acid(H2BDC)(0.20mmol), phenanthrene-9,10-dione(pheno)(0.10mmol)and NaOH (0.20mmol)in water(10mL)was sealed in a18mL Te?on lined stainless steel container and heated at150°C for72h.The reaction product was dark yellow block crystals of1,which were washed by deionized water sev-eral times and collected by?ltration;Yield,78%. Elemental Analysis:Calcd.for C24H15N2O10Zn2:C,46.33;H,2.43;N,4.50%.Found:C,46.38;H,2.47;N,4.48%.IR (KBr pellet),cm-1(intensity):3437(br),3062(m),1587(s),1523(m),1491(w),1424(m),1391(s),1226(w),1147 (w),1103(w),1051(w),875(w),843(m),740(w),728 (m),657(w).2.3X-ray Structure DeterminationThe crystallographic data collections for complex1were carried out on a Bruker Smart Apex II CCD with graphite-monochromated Mo-K a radiation(k=0.71073A?)at 293(2)K using the x-scan technique.The data were inte-grated by using the SAINT program[14],which also did the intensities corrected for Lorentz and polarization effects.An empirical absorption correction was applied using the SADABS program[15].The structures were solved by direct methods using the SHELXS-97program; and,all non-hydrogen atoms were re?ned anisotropically on F2by the full-matrix least-squares technique using the SHELXL-97crystallographic software package[16,17]. The hydrogen atoms were generated geometrically.All calculations were performed on a personal computer with the SHELXL-97crystallographic software package[17].The details of the crystal parameters,data collection and re?nement for four compounds are summarized in Table1. Selected bond lengths and bong angles for complex1are listed in Table2.3Results and DiscussionThe X-ray diffraction study for1reveals that the material crystallizes in the orthorhombic space group Pbca and features a2-fold parallel interpenetrated3D?3D net-work motif.The asymmetric unit contains two Zn(II) atoms,one hydroxyl,one pheno ligand,one and half of p-BDC molecules and one solvent water molecule.Selected bond lengths for1are listed in Table2.As shown in Fig.1, the Zn1ion,which is in the center of a tetrahedral geom-etry,is surrounded by three carboxylic oxygen atoms (Zn–O=1.918(5)–1.964(5)A?)from three p-BDC ligands and one l3-OH oxygen atom(O9).The Zn–O distance is1.965(5)A?.Two nitrogen atoms(N1and N2)that belong to pheno,one p-BDC oxygen atom(O3A)and one hydroxyl oxygen atom(O9A)are ligated to the Zn2center in the equatorial plane with another oxygen atom(O9)that arises from the second hydroxyl group and one oxygen atom(O5)that arises from the second p-BDC molecule situated in the axial position.EachZn2lies approximately in the equatorial position with a maximum deviation (0.048A?)from the basal plane.In the structure,Zn–O and Zn–N bond distances are in the range of 2.0530(5)–2.112(5)and2.157(5)–2.184(2)A?,respectively. There exist two types of p-BDC found in1(Scheme1); namely,monobidentate bridging(l3)and bi-bidentatebridging(l4)coordination modes.The bidentate bridging p-BDC connects mixed metals,where the smallest ZnáááZn distance is3.163A?,to complete a homodinuclear cluster, which is further linked by l3-OH into a six-connected Table1Crystal data and summary of X-ray data collection for1Zn2(pheno)(OH)(BDC)1.5áH2O Empirical formula C24H15N2O10Zn2Molecular mass/g mol-1622.12Color of crystal Dark yellowCrystal fdimensions/mm0.1890.1690.12 Temperature/K293Lattice dimensionsa/A?18.777(9)b/A?13.657(6)c/A?19.983(9)a/°90b/°90c/°90Unit cell volume(A?3)5125(4)Crystal system OrthorhombicSpace group PbcaZ8l(Mo-K a)/mm-1 1.931D(cacl.)/g cm-3 1.613Radiation type Mo-K aF(000)2504Limits of data collection/° 2.04B h B25.05Total re?ections24155Unique re?ections,parameters4545,347No.with I[2r(I)2821R1indices[I[2r(I)]0.0657w R2indices0.1858Goodness of?t 1.060Min/max peak(Final diff.map)/e A?-3-0.658/2.322tetranuclear cluster that is jointly coordinated by six p-BDC molecules(Fig.2).The clusters are further extended by p-BDC into a single3D framework(Fig.3).For clarity, we used the topological method to analyze this3D framework.Thus,the six-connected SBU is viewed to be a six-connected node.Furthermore,based on consideration of the geometry of thisnode,the3D frame is classi?ed as an a-Po net with41263topology(Fig.4).Of particular interest,the most intriguing feature of complex1is that a pair of identical3D single nets is interlocked with each other,thus directly leading to the formation of a2-fold interpenetrated3D?3D architecture(Fig.4)and the two pcu(a-Po)frameworks are related by a screw axis21[18]. Recently,a complete analysis of3D coordination networks shows that more than50interpenetrated pcu(a-Po)frames have been documented in the CSD database[18],including 2-fold,3-fold[19],and4-fold[20]interpenetration.In addition,several non-interpenetration motifs with a-Po topology have been reported to date[21].ZnZnO ZnZnZnZnO Znbidentate bidentate bidentate monodentateI IIScheme1Coordination modesof the bdc ligands in the structure of1;I is bis(bidentate),II is bi/monodentateFig.1ORTEP representation of complex1(the H atoms have been omitted for the sake of clarity).The thermal ellipsoids are drawn at 30%probabilityTable2Selected bond lengths(A?)and angles(°)for1Symmetry transformations usedto generate equivalent atoms:#1x-1/2,y,-z+1/2;#2-x,-y+1,-z;#3-x+1/2,-y+1,z-1/2Zn(1)–O(1) 1.918(5)Zn(2)–O(9)#2 2.091(4)Zn(1)–O(4)#1 1.953(5)Zn(2)–O(9) 2.103(5)Zn(1)–O(6) 1.964(5)Zn(2)–O(3)#3 2.112(5)Zn(1)–O(9) 1.965(5)Zn(2)–N(1) 2.157(6)Zn(2)–O(5)#2 2.053(5)Zn(2)–N(2) 2.184(6)O(1)–Zn(1)–O(4)#197.9(2)O(9)–Zn(2)–O(3)#388.81(18)O(1)–Zn(1)–O(6)112.9(2)O(5)#2–Zn(2)–N(1)94.7(2)O(4)#1–Zn(1)–O(6)104.7(2)O(9)#2–Zn(2)–N(1)170.7(2)O(1)–Zn(1)–O(9)122.9(2)O(9)–Zn(2)–N(1)91.6(2)O(4)#1–Zn(1)–O(9)109.7(2)O(3)#3–Zn(2)–N(1)88.9(2)O(6)–Zn(1)–O(9)107.0(2)O(5)#2–Zn(2)–N(2)87.1(2)O(5)#2–Zn(2)–O(9)#291.9(2)O(9)#2–Zn(2)–N(2)98.3(2)O(5)#2–Zn(2)–O(9)173.72(19)O(9)–Zn(2)–N(2)94.5(2)O(9)#2–Zn(2)–O(9)81.82(19)O(3)#3–Zn(2)–N(2)164.3(2)O(5)#2–Zn(2)–O(3)#391.3(2)N(1)–Zn(2)–N(2)75.7(2)O(9)#2–Zn(2)–O(3)#397.42(19)Fig.2Polyhedral representation of the homotetranuclear unit as asix-connected node linked by p-BDC ligandsMoreover,rich inter and intra hydrogen-bonds between the water molecules and the carboxylate groups (Table 3)further strengthen the stacking of the supra-architecture (Fig.5).4Supplementary MaterialsCrystallographic data (excluding structure factors)for thestructures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supple-mentary publication /doc/c97a12ccf61fb7360b4c65f3.html DC-666555.Copies of the data can be obtained free of charge on application to CCDC,12Union Road,Cambridge CB21EZ,UK (Fax:+44-1223-336033;e-mail:deposit@/doc/c97a12ccf61fb7360b4c65f3.html ).Acknowledgments This work was supported by the National Nat-ural Science Foundation of China (20731004)and the Natural Science Foundation of the Education Committee of Anhui Province,China(KJ2008B004).Fig.3Polyhedral presentation of one set of the 3D network along a -axis (a )and b -axis (b )Table 3Distance (A ?)and angles (°)of hydrogen bonding for com-plex 1D–H áááADistance of D áááA (A ?)Angle of D–H–A (°)O1W–H1WB áááO2#1 2.677(9)164O9–H19áááO1W#2 2.841(9)151C13–H13áááO3#3 3.045(10)121C22–H22áááO1W#43.353(10)167Symmetry transformations used to generate equivalent atoms:#1x,y,1+z;#2-x,1-y,-1+z;#3-x+1/2,-y+1,z -1/2;#4-x,1-y,1-zFig.4Simpli?ed schematic representation of the 3D ?3D two-fold interpenetrated a -Po network in1Fig.5Projection of the structure of 1along b -axis (dotted lines represent hydrogen-bonding)References1.(a)P.J.Hagrman,D.Hagrman,J.Zubieta,Angew.Chem.Int.Ed.38,2638(1998);(b)S.Leininger,B.Olenyuk,P.J.Stang,Chem.Rev.100,853(2000);(c)A.Erxleben,Coord.Chem.Rev.246, 203(2003);(d)K.Biradha,Y.Hongo,M.Fujita,Angew.Chem. Int.Ed.39,3843(2000);(e)P.D.Harey,H.B.Gray,J.Am.Chem.Soc.110,2145(1988);(f)D.Cave,J.M.Gascon,A.D.Bond,S.J.Teat,P.T.Wood,/doc/c97a12ccf61fb7360b4c65f3.html mun.1050(2002);(g)F.A.AlmeidaPaz,J.Klinowski,Inorg.Chem.43,3882(2004);(h)K.Biradha, Y.Hongo,M.Fujita,Angew.Chem.Int.Ed.39,3843(2000);(i) M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.O’Ke-egge,O.M.Yaghi,Science295,469(2002);(j)S.Q.Zhang,R.J. Tao,Q.L.Wang,N.H.Hu,Y.X.Cheng,H.L.Niu,W.Lin,J.Am.Chem.Soc.123,10395(2001);(k)L.Carlucci,G.Ciani,D.M.Proserpio,Cryst.Growth Design5,37(2005)2.(a)M.Eddaoudi,D.B.Moler,H.Li,B.Chen,T.M.Reineke,M.O’Keeffe,O.M.Yaghi,Acc.Chem.Res.34,319(2001);(b)P.J.Hagrman,D.Hagrman,J.Zubieta,Angew.Chem.Int.Ed.38, 2638(1999);(c)O.R.Evans,W.Lin,Acc.Chem.Res.35,511 (2002);(d)S.Kitagawa,R.Kitaura,S.Noro,Angew.Chem.Int.Ed.43,2334(2004);(e)S.L.James,Chem.Soc.Rev.32,276 (2003);(f)L.Pan,H.Liu,X.Lei,X.Huang,D.H.Olson,N.J.Turro,J.Li,Angew.Chem.Int.Ed.42,542(2003)3.(a)G.Ferey,C.Mellot-Draznieks,C.Serre,/doc/c97a12ccf61fb7360b4c65f3.html lange,Acc. Chem.Res.38,217(2005);(b)M.Eddaoudi,J.Kim,J.B.Wachter,H.K.Chae,M.O’Keeffe,O.M.Yaghi,J.Am.Chem.Soc.123,4368(2001);(c)M.Eddaoudi,J.Kim,M.O’Keeffe, O.M.Yaghi,J.Am.Chem.Soc.124,376(2002);(d)A.Thiru-murugan,S.Natarajan,Cryst.Growth Design6,983(2006);(e) R.Murugavel,M.G.Walawalkar,M.Dan,H.W.Roesky,C.N.R. Rao,Acc.Chem.Res.37,763(2004)4.(a)J.Kim,B.Chen,T.M.Reineke,H.Li,M.Eddaoudi,D.B.Moler,M.O’Keeffe,O.M.Yaghi,J.Am.Chem.Soc.123,8239 (2001);(b)J.J.Lu,A.Mondal,B.Moulton,M.Zaworotko,An-gew.Chem.Int.Ed.40,2113(2001)5.(a)Q.R.Fang,X.Shi,G.Wu,G.Tain,G.S.Zhu,R.W.Wang,S.L.Qiu,J.Solid State Chem.176,1(2003);(b)H.Li,C.E.Davis,T.L.Groy,D.G.Kelley,O.M.Yaghi,J.Am.Chem.Soc.120,2186(1998)6.(a)M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.O’Keeffe,O.M.Yaghi,Science295,469(2002);(b)B.Kesanli,Y.Cui,M.R.Smith,E.W.Bittner,B.C.Bockrath,W.B.Lin, Angew.Chem.Int.Ed.44,72(2005)7.Q.R.Fang,G.S.Zhu,Z.Jin,M.Xue,X.Wei,D.J.Wang,S.L.Qiu,Cryst.Growth Design7,1035(2007)8.C.Lei,J.G.Mao,Y.Q.Sun,H.Y.Zeng,A.Clear?eld,Inorg.Chem.42,6157(2003)9.J.R.Li,Y.Tao,Q.Yu,X.H.Bu,/doc/c97a12ccf61fb7360b4c65f3.html mun.1527(2007)10.S.Y.Yang,L.S.Long,R.B.Huang,L.S.Zheng,/doc/c97a12ccf61fb7360b4c65f3.html mun.472(2002)11.T.M.Reineke,M.Eddaoudi,D.M.Moler,M.O’Keeffe O.M.Yaghi,J.Am.Chem.Soc.122,4843(2002)12.D.M.Proserpio,R.Hoffman,P.Preuss,J.Am.Chem.Soc.116,9634(1994)13.(a)O.Ermer,Adv.Mater.3,608(1991);(b)/doc/c97a12ccf61fb7360b4c65f3.html ler,Adv.Mater.13,525(2001)14.SAINT version6.02a,Software Reference Manual(Bruker AXSInc.,Madison,W1,2002)15.G.M.Sheldrick,SADABS:Program for Empirical AbsorptionCorrection of Area Detector Data(University of Go¨ttingen, 1996)16.G.M.Sheldrick,SHELXS-97:Program for Crystal StructureSolution(University of Go¨ttingen,1997)17.G.M.Sheldrick,SHELXL-97:Program for Crystal StructureRe?nement(University of Go¨ttingen,1997)18.V.A.Blatov,L.Carlucci,G.Ciani,D.M.Proserpio,Cryst.Eng.Comm.6,377(2004)19.(a)B.F.Hoskins,R.Robson,N.V.Y.Scarlett,J.Chem.Soc./doc/c97a12ccf61fb7360b4c65f3.html mun.2025(1994);(b)E.Siebel,R.D.Fischer,Chem. Eur.J.3,1987(1997);(c)B.F.Abrahams,B.F.Hoskins,R.Robson,D.A.Slizys,/doc/c97a12ccf61fb7360b4c65f3.html m.4,478(1997);(d)M.J. Plater,M.R.S.J.Foreman,J.M.S.Skakle,Cryst.Eng.4,293 (2001);(e)X.L.Wang,C.Qin,E.B.Wang,Z.M.Su,Chem.Eur. J.12,2680(2006)20.B.Kesanli,Y.Cui,R.Smith,E.Bittner,B.C.Bockrath,W.Lin,Angew.Chem.Int.Ed.117,74(2005)21.(a)H.L.Gao,L.Yi,B.Ding,H.S.Wang,P.Cheng,D.Z.Liao,S.P.Yan,Inorg.Chem.45,481(2006);(b)Y.H.Wen,J.Zhang, X.Q.Wang,Y.L.Feng,J.K.Cheng,Z.J.Li,Y.G.Yao,New J. Chem.29,995(2005);(c)H.L.Sun,B.Q.Ma,S.Gao,S.R.Batten,Cryst.Growth Design5,1331(2005);(d)J.Yang,J.F.Ma,Y.Y.Liu,S.L.Li,G.L.Zheng,Eur.J.Inorg.Chem.2174 (2005)。

化学课程英文名称对照表

[英语学习]化学专业英语前言翻译

Reactions between hexanuclear manganese pivalate with lanthanide salts (chlorides or nitrates), in the presence of potassium hydroxide, 2-pyridylmethanol and sodium azide leads to formation of a new family of hexaheteronuclear manganese–lanthanide clusters.4.AbstractTwo novel metal–organic frameworks of [M3(ptz)2(N3)4(H2O)2] (M = Zn(1), Cd(2)) (ptz =5-(4-pyridyl)tetrazolate) have been prepared hydro(solvo)thermally by reactions of 4-cyanopyridine and excess NaN3 in the presence of zinc and cadmium chloride, respectively. The overall structure motif of complexes 1 and 2 show pillared layered frameworks and feature an unprecedented 3-nodal network with (3,5,6)-connectivity. The layer is of particular interest as it is constructed by μ1,1–N3− and μ1,1,3–N3−bridging modes, simultaneously. Furthermore, the solid fluorescent properties and TGA were studied.5. AbstractStructural characterization of a new self assembled coordination polymer of Cu II, hexamine (hmt) and benzoate (OBz), [Cu4(OBz)8(hmt)]n (1), reveals that it is a cubic non-interpenetrating diamondoid network formed by the coordination of the μ4-hmt ligand to a linear [Cu2(OBz)4] spacer. The magnetic study reveals that the Cu(II) ions are antiferromagnetically coupled (J = − 323.5 cm−1) through the syn–syn carboxylate bridges.6. AbstractSimple PET chemosensors based on anthracene show a selective turn-on fluorescence sensing for Cu2+. The flexible receptor is favorable for turn-on sensing due to chelation enhanced fluorescence. Interestingly, the turn-on fluorescence sensing for Cu2+ is hardly disturbed by the competitive cations and other highly prevalent species in biological and environmental systems, implying a potential in the biological and environmental applications.Metallacyclodimeric complex of [(Me4en)Pd(L)]2(PF6)4 (Me4en = N,N,N′,N′-tetramethylethylenediamine; L = 1,3-bis(4-pyridyl)tetramethyldisiloxane) is a sensitive container for dioxane via appropriate size effect. The equilibrium between the “included” and “free” dioxane species has been monitored by temperature-dependent 1H NMR spectra.8. AbstractAn unprecedented (ethanol)4 cluster is observed in a photoluminescent silver(I) coordination polymer host, [Ag2(dmt)2(nda)·2EtOH]n (1, dmt = 2,4-diamino-6-methyl-1,3,5-triazine, H2nda =naphthalene-1,4-dicarboxylic acid, EtOH = ethanol). In 1, two pairs of symmetry-related ethanol molecules are hydrogen bonded with each other by OH⋯O hydrogen bonds to form a R44(8) hydrogen bond motif where all the ethanol molecules are proton acceptor and proton donor at the same time. The thermal stability and luminescent behavior of 1 were also discussed.9. AbstractA new 3D sandwich-type MOF named [Zn3(bptc)(H2O)4]·C2H5OH·2H2O (1) (H4bptc =biphenyl-2,5,2',5'-tetracarboxylic acid) was obtained by solvothermal reaction, which represents a rare trinodal (3, 4, 10)-connected topology network. Moreover, the thermal stability, UV–vis absorption spectra and photoluminescent properties of 1 have been investigated as well.10. AbstractThe synthesis and characterization of novel metal-free and cobalt phthalocyanine, peripherally symmetrically derived from2,3,6,7,10,11,13,14-octahydro-5H,9H-4,12-(propanothiopropano)-1,8,15,23,4,12-benzotetrathiodiazacyc loheptadecane-17,18-dicarbonitrile (4) which was prepared by the reaction of1,9-diaza-5,13-dithiocyclohexadecane (3) and 1,2-bis(2-iodoethylmercapto)-4,5-dicyanobenzene (2) wascarried out. The novel compounds were characterized by using elemental analysis, 1H, 13C NMR, IR,UV–vis and MS techniques.11. AbstractA novel cationic dinuclear ruthenium complex [RuCl(HL)(TFTPP)]2 (H2L =2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine; TFTPP = tri(p-trifluoromethylphenyl)phosphine) has been synthesized and characterized by 31P{1H} NMR, 1H NMR, elemental analysis and X-ray crystallography. This complex is the first cationic dinuclear ruthenium complex bearing N4 ligand characterized by single crystal X-ray analysis. It exhibits good catalytic activity for the transfer hydrogenation of ketones in refluxing 2-propanol.12. AbstractThree new metal-organic coordination polymers, [Mn(4,4′-bpy)(H2BTCA)(H2O)2](4,4′-bpy) (1),[Na2Co(BTCA)(OXA)]·3H2O (2) and [Na2Co(BTCA)(H2O)2] (3), (H4BTCA =benzene-1,2,4,5-tetracarboxylic acid, H2OXA = oxalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. Complex 1 possesses a 3D polymeric structure, which is comprised of (4,4)-layers. Hydrogen bonds play a dominant role in the construction of the final 3D supramolecule. 1D channels are observed in complex 2, which can be ascribed to pillared-layer motifs.13. AbstractTwo 2-(2-benzimidazolyl)-6-methylpyridine (Hbmp) copper(I) complexes bearing PPh3 and1,4-bis(diphenylphosphino)butane (dppb), namely, [Cu(Hbmp)(PPh3)2](ClO4) (1) and[Cu(Hbmp)(dppb)](ClO4) (2), have been synthesized. X-ray diffraction analysis reveals that the most significant influence of the phosphine ligands on the structures is on the P–Cu–P bond angle. Both two Cu(I) complexes exhibit a weak low-energy absorption at 360–450 nm, ascribed to the Cu(I) to Hbmp metal-to-ligand charge-transfer (MLCT) transition, perhaps mixed with some ILCT character inside Hbmp.The room-temperature luminescences are observed for 1 and 2, both in solution and in the solid state, which originate from the MLCT excited states and vary markedly with the phosphine ligands.14. AbstractA new self-assembly gadolinium(III)–iron(II) complex (Gd2Fe) was synthesized and characterized. Relaxivity studies showed that complex Gd2Fe exhibited higher relaxation efficiency compared with the clinically used Gd-DTPA. In vitro MR images on a 0.5 T magnetic field exhibited a remarkable enhancement of signal contrast for Gd2Fe than Gd-DTPA. The results indicated that Gd2Fe could serve as a potential MRI contrast agent.15. AbstractThe reaction of AgClO4·6H2O with (+/−)-trans-epoxysuccinic acid (H2tes) in the presence of2,6-dimethylpyridine afforded a three-dimensional (3-D) Ag I coordination polymer [Ag2(tes)]∞ (1), which exhibits an unusual 5-connected self-penetrating (44·66)2 topological net (tes =(+/−)-trans-epoxysuccinate). Comparison of the structural differences with our relevant finding, atwo-dimensional (2-D) (4,8)-connected (45·6)2(418·610) coordination polymer [Ag4(ces)2]∞ (S1) (ces =cis-epoxysuccinate), suggests that the carboxyl configuration on the ternary ring backbone of H2tes or H2ces ligand plays an important role in the construction of coordination networks.16. AbstractAn unusual three-dimensional (3D) pillared-layer 3d–4f (Cu+–Sm3+) heterometallic coordination polymer, {Sm2Cu7Br6(IN)7(H2O)5·3H2O}n (1) (HIN = isonicotinic acid), has been successfully synthesized by hydrothermal reaction of Sm2O3, CuBr2, HIN, HClO4 and H2O, and characterized by elemental analyses, IR, PXRD, and single-crystal X-ray diffraction. The structure determination reveals that 1 possesses 3D heterometallic framework constructed upon unprecedented [Cu7Br6]n n+ inorganic layers linked by dimeric Sm2(IN)6 pillars. Additionally, the thermogravimetric analysis and luminescent property of 1 were investigated and discussed.17. AbstractA novel double-Dawson-anion-templated, triangular trinuclear Cu-trz unit-based metal–organic framework [Cu II8(trz)6(μ3-O)2(H2O)12][P2W18O62]·4H2O (1) (Htrz = 1,2,4-triazole), has been hydrothermally synthesized and characterized by routine methods. Compound 1 is the first example of the Cu3-triad triangular unit-based three-dimensional (3D) metal–organic framework templated by double [P2W18O62]6−polyoxoanions. Furthermore, the electrochemical property of compound 1 has been studied.18. AbstractA new three-dimensional terbium-carboxylate framework [Tb4L3(H2O)9]·7H2O (1) [(H4L =4,4′-(hexafluoroisopropylidene)diphthalic acid)] has been hydrothermally synthesized and structurally characterized. The framework contains Tb2 and Tb4 clusters, and exhibits an unprecedented 4-nodal (3,4,5,8)-connected topology. In addition, the thermogravimetric analysis, luminescent and magnetic properties were investigated.19. AbstractThis paper reports two alkaline-earth metal phosphonates with formulae M(4-cppH2)2 [M = Sr (1), Ba (2); 4-cppH3 = 4-carboxylphenylphosphonic acid]. Compound 1 shows a chain structure made up ofedge-sharing {SrO8} polyhedra and {PO3C} tetrahedra. While in compound 2, the edge-sharing {BaO8} polyhedra are connected by the {PO3C} tetrahedra to form a two-dimensional inorganic layer. Neighboring chains in 1 or layers in 2 are cross-linked by hydrogen bond interactions between the protonated carboxylate groups, resulting in three-dimensional supramolecular structures. The magnesium alloys coated with 1 or 2 films show significantly improved anti-corrosion behaviors compared to the bare substrate.20. AbstractA novel 3D inorganic–organic hybrid compound {[Cu3(en)(TTHA)(H2O)42O}n(1) (TTHA =1,3,5-triazine-2,4,6-triamine hexaacetic acid; en = ethylenediamine) has been synthesized andcharacterized. Topological analysis shows that the compound is a new 3,10-connected 2-nodal net with point symbol (418.624.83)(43)2, further simplification of the structure by merging two 3-connected nodes and one 10-connected node together gives a rare uninodal 8-connected hex net, we conclude that the2-nodal net found in the network is a hex-originated supernet. TG, IR, PXRD and photoluminescent spectra of the compound 1 are investigated.21. AbstractUnder hydrothermal conditions, Sm(NO3)3·6H2O reacts with N-(2-Hydroxyethyl)iminodiacetic acid(H3heidi), oxalic acid (H2Ox), in the presence of NiCl2·6H2O and NaOH, producing a novel two dimensional coordination polymer with the empirical formula of Na[Sm(Hheidi)(Ox)]·2H2O (1). X-ray diffraction analyses show that 1 crystallizes in the orthorhombic system, P na21 space group, a =25.9008(19) Å, b = 6.2593(5) Å, c = 8.7624(6) Å, in which the network of SmNO8 and oxalate units forms an extended two dimensional layered structure. To the best of our knowledge, 1 represents the first structurally characterized lanthanide complex containing H3heidi ligand. The variable-temperature magnetic property of 1 has been investigated and the results of magnetic determination suggest the existence of a weak antiferromagnetic coupling between the samarium ions.22. AbstractHeating [WO2(S2CNBu i2)2] with a slight excess of ArNCO (Ar = Ph, p-tolyl) results in the rapid formation of imido-ureato complexes [W(NAr){κ2-ArNC(O)NAr}(S2CNBu i2)2], a transformation believed to occur via the bis(imido) intermediates [W(NAr)2(S2CNBu i2)2]. The ureato ligand is easily removed (as the urea) upon addition of gaseous HCl to afford the dichloride [W(NAr)Cl2(S2CNBu i2)2]. While bis(imido) complexes are unavailable from the direct reaction of isocyanates (or amines) with [WO2(S2CNBu i2)2], they can be prepared upon addition of dithiocarbamate salts to [W(NBu t)2(NHBu t)2] addition of two equivalents of [NH2Bu i2][Bu i2NCS2] affording [W(NBu t)2(S2CNBu i2)2] in which both imido groups are linear.23. AbstractA new neutral dimeric cyclometalated iridium complex containing bridging thiocyanate ligands,[{Ir(μ-SCN)(pqcm)2}2] (1, pqcmH = 2-phenyl-quinoline-4- carboxylic acid methyl ester), has been synthesized and structurally characterized. The photoluminescence (PL) spectrum of 1 shows emission maximum at 638 nm with a lifetime of 0.11 μs and the PL quantum yield is c. The phosphorescence behaviours of 1 towards different solvents and metal ions were also investigated and the strong phosphorescence quenching by acetonitrile and two equivalents of Hg2+, Cu2+ and Ag+ ions were observed.24. AbstractIonothermal reaction of isophthalate (H2ip), and colbolt(II) nitrate under 1-ethly-3-methylimidazolium bromide (EMimBr) as solvent leads to a novel three dimensional metal–organic framework(EMim)2[Co3(ip)4] (1). It can be described as an eight-connected CsCl-type net (42464) utilizing trinuclear Co(II) clusters as eight-connected nodes and ip ligands as linkers. The imidazolium cation [EMim]+ of the ionic liquid acting as charge-compensating agents has interactions with the framework. The magnetic properties studies show ferrimagnetic behavior for 1.25. AbstractUsing the deprotection–realkylation methodology, a new electroactive tetrathiafulvalene-based bipyridine ligand,5-[{2-[4,5-Bis(methylthio)-1,3-dithiol-2-ylidene]-5-(methylthio)-1,3-dithiol-4-yl}thio]-methyl-2,2′-bipyridine (L), has been synthesized. Reactions of the above ligand with Re(CO)5Br or Re(CO)5Cl afford the corresponding tricarbonyl rhenium(I) complexes ReL(CO)3X (X = Br, 1; X = Cl, 2), respectively. Crystal structures of 1 and 2 have been described. The absorption properties of these new compounds have been studied. Electrochemical measurements have been performed and TTF/TTF+•/TTF2+ redox processes are observed.26. AbstractThree carbon-bridged bis(phenolate) neodymium complexes, [(MBMP)2Nd(μ3–Cl)Li(THF)2Li(THF)] (1), [(MBBP)2Nd(μ3-Cl)Li(THF)2Li(THF)] (2) and [(THF)2Nd(EDBP)2Li(THF)] (3) have been synthesized by one-pot reaction of NdCl3 and LiCH2SiMe3with 6,6′-methylenebis(2-tert-butyl-4-methylphenol)(MBMP-H2), 6,6′-methylenebis(2,4-di-tert-butylphenol) (MBBP-H2) or 6,6′-(ethane-1,1-diyl)bis(2,4-di-tert-butylphenol) (EDBP-H2), respectively, in a molar ratio of 1:4:2. The definitive structures of complexes 2 and 3 were determined by X-ray diffraction studies. Experimental results show that 1–3 efficiently initiate the ring-openin g polymerization (ROP) of ε-caprolactone and ROP of L-lactide.27. AbstractA 3D metal-organic framework {[Cd2(TZ)3(BDC)]·5H2O}n (1·5nH2O) (HTZ = 1H-tetrazole, H2BDC =1,4-benzenedicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The phase purity was confirmed by powder X-ray diffraction (PXRD), and the stability was identified by thermal gravimetric analysis (TG) and variable-temperature powder X-ray diffraction (VT-PXRD). The result of the single-crystal X-ray diffraction analysis indicates that 1 is a novel 3D microporous metal-organic framework constructed from Cd(II) metal centers and mixed linkers of TZ−anions and BDC2− anions. Photoluminescent measurement elucidates that 1 displays a strong and broad emission peak at 423 nm, which suggests that 1 may be a potential purple-light material.28. AbstractTwo inorganic–organic hybrids, (MPDA)2n(Pb3I10)n (MPDA = p-Me3NC6H4NMe3) (1) and(H2EPDA)n(Pb2I6)n·2n H2O (H2EPDA = p-Et2NHC6H4NHEt2) (2), have been solvothermally synthesized using p-phenylenediamine (PDA) as a precursor. Their iodoplumbate ions all show 1-D chain structures, but differ in interlinkage modes of [PbI6] octahedra: the former is both face- and edge-sharing, while the latter is face-sharing. The chain-like structure in 1 was reported only once in the literature. The results of optical absorption spectra and theoretical calculations for compounds PbI2 and 1–2 reveal a quantum confinement effect. Photoluminescent analyses show that they all exhibit blue emissions upon UV irradiation, which mainly originate from charge transfer from iodine atoms to ammoniums.29. AbstractPlatinum(II) complexes, [Pt(PDTC)(H2O)Cl] and [Pt(PDTC)(DMSO)Cl] (1) (PDTC = pyrrolidinedithiocarbamate) have been prepared and characterized by IR, NMR and X-ray crystallographic methods. In the crystal structure of 1 the central platinum atom is coordinated to two sulfur atoms of PDTC, one sulfur atom of DMSO and one chloride ion adopting a square planar geometry with the average cis and trans bond angles of 90.00° and 171.62° respectively. The 1H and 13C NMR spectral data indicate the coordination of both PDTC and DMSO to platinum(II). The title complex was screened for antimicrobial effects and the results show that it exhibits significant activity againstgram-negative bacteria (E. coli, P. aeruginosa), while the activities are moderate against molds (A. niger, P. citrinum) and yeasts (C. albicans, S. serevisaiae).30. AbstractA new stable mixed-ligand metal organic framework Zn2(tpt)2(2-atp)I21 (tpt = tris (4-pyridyl) triazine, 2-atp = 2-aminoterephthalate) with split channels has been synthesized and characterized. The nitrogen containing ligands tpt and 2-atp are selected to create attractive basic sites for the catalyst. The Knoevenagel condensation between benzaldehyde and the active hydrogen compound (ethyl cyanoacetate or malononitrile) is carried out using compound 1 as solid basic catalytic support. The test results indicate that 1 is an efficient base catalyst with selective catalytic properties. It gives 37% and 99% yield respectively for the condensation products ethyl (E)-α-cyanocinnamate and2-benzylidenemalononitrile. TG data show that the solid catalyst sample is fairly thermally stable. The compound does not show any signs of decomposition until 420 °C. PXRD data support that the catalyst remains its crystalline and framework stability after the catalysis process. These characters make it easily to be regenerated for the next cycle.31. AbstractA heteroleptic nickel-bis-1,2-dithiolene ion–pair complex, [BzQl][Ni(dmit)(mnt)] (where BzQl+ =1-(benzyl)quinolinium; dmit2− = 2-thioxo-1,3-dithiole-4,5-dithiolate, mnt2− = maleonitriledithiolate), was synthesized and characterized structurally, which exhibited novel magnetic bistability. The compound crystallized in triclinic system with space group P-1. The anions and cations form alternating layered alignments, and the anionic layer is built by the irregularly heteroleptic [Ni(dmit)(mnt)]− chains, where theneighboring anions are connected via lateral-to-lateral S…S contacts of dmit2− ligands. The temperature dependences of magnetic susceptibility follow the S = ½ Heisenberg alternating linear-chain model in high-temperature phase and Curie–Weiss law in low-temperature phase.32. AbstractA novel two-dimensional (2D) Mn(II) coordination polymer [Mn(H2bdc)(DMA)2] (1; H2bdc = terephthalic acid; DMA = N,N′-dimethylacetamide) based on trinuclear manganese subunit has been solvothermally prepared and structurally characterized by single-crystal X-ray diffraction. Compound 1 exhibits a rare layered structure with 6-connected hxl topology constructed from the trinuclear Mn3(COO)6 units, and further stacking of layers leads to a 3D supramolecular framework. The thermalgravimetric behavior and magnetic property of 1 have been also investigated. The magnetic susceptibility measurements reveal that the compound exhibits antiferromagnetic coupling interactions.33. AbstractA new salicylaldehyde derivative 1, i.e. 5-chloro-3-(ethoxymethyl)-2-hydroxybenzaldehyde, has been prepared and structurally characterized. A novel dinuclear copper(II) complex of its air-oxidized product 2 has been successfully yielded from the in situ copper(II) ion catalysis and complexation. Additionally, another control experiment has been carried out by using 3,5-dibromo-2-hydroxybenzaldehyde as the starting material, and a similar mononuclear air oxidation copper(II) complex 3 is obtained, where3,5-dibromo-2-hydroxybenzaldehyde has also been in situ transformed to the divalent anion of3,5-dibromo-2-hydroxybenzoic acid.34. AbstractSelf-assembly of CdCl2 and 1,2,4-triazole under hydrothermal condition yields a novel three-dimensional coordination polymer, namely {[Cd8Cl4(Trz)12(H2O)]·2H2O}n (1) (Trz = 1,2,4-triazole). Single-crystal X-ray diffraction reveals that four of the five independent Cd centers are linked by two μ2-Cl and two μ3-Cl atoms to form novel heptanuclear [Cd7Cl4] clusters, which are connected by the bridging water molecules to generate an unprecedented 1D castellated inorganic chain. Furthermore, the fifth unique Cd centerand the castellated Cd–Cl–O chain are joint to each other via six different μ3-Trz ligands to give a 3D organic–inorganic hybrid framework of 1.。

舒兴田机会-S.H

沸石分子筛
沸石分子筛（以下简称分子筛），其骨架主要是由沸石分子筛（以下简称分子筛），其骨架主要是由硅、铝、磷、钛、锡、硼、锗、镓等元素的原子组成，彼此通过与氧键合，构建成晶内具有丰富空间（多孔）、在很多情况下包含可交换阳离子、结构多种多样的一类无机结晶材料。因为这类多孔材料的孔径一般＜2nm,落在分子尺度范围内，有筛选分子的特性，所以又称之谓分子筛。
图. L酸与质子酸OH相互作用提升H+酸强度
Chem. Soc. Rev., 2014, 43, 7548--7561
分子筛材料的特点
此外，分子筛结构的不同限域作用也会影响酸性强

度；特别是孔口在 12-员环以下分子筛的近刚性结构，表现出优异的耐热和耐水热的结构稳定性。以上这些特点是分子筛在工业催化、吸附分离，包括膜分离、离子交换、封装（均相催化载持、光学材料、无机颜料）等领域得到广泛应用的根本原因。
分子筛骨架结构类型数目
到2014年8月国际分子筛协会结构委员会批准分子筛骨架结构类型数总量增加到218种。
分子筛骨架结构类型数目

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Type material: ITQ-52 Simancas, R., Jorda, J.L., Rey, F., Corma, A., Cantin, A., Peral, I. and Popescu, C. "A New Microporous Zeiolitic Silicoborate (ITQ-52) with interconnected Small and Medium Pores" J. Am. Chem. Soc. 136, 3342-3345 (2014) IFY Type material: ITQ-50 Jorda, J.L., Rey, F., Sastre, G., Valencia, S., Palomino, M., Corma, A., Segura, A., Errandonea, D., Lacomba, R., Manjon, F.J., Gomis, O., Kleppe, A.K., Jephcoat, A.P., Amboage, M. and Rodriguez-Velamazan, J.A. "Synthesis of a of a Novel Zeolite through a PressureInduced Reconstructive Phase Transition Process" Angew. Chem. Int. Ed. 52, 10458-10462 (2013) *-ITN Type material: ITQ-39 Wilhammar, T., Sun, J., Wan, W., Oleynikov, P., Zhang, D., Zou, X., Moliner, M., Gonzalez, J., Martinez, C., Rey, F. and Corma, A. "Structure and catalytic properties of the most complex intergrown zeolite ITQ-39 determined by electron crystallography" Nature Chem. 4, 188-194 (2012) IRN Type material: ITQ-49 Hernandez-Rodriguez, M., Jorda, J. L., Rey, F. and Corma, A. "Synthesis and Structure Determination of a New Microporous Zeolite with Large Cavities Connected by Small Pores" J. Am. Chem. Soc. 134, 13232-13235, (2012) POS Type material: PKU-16 Hua, W., Chen, H., Yu, Z.-B., Zou, X., Lin, J. and Sun, J. “A Germanosilicate Structure with 11x11x12-Ring Channels Solved by Electron Crystallography”（中国） Angew. Chem. Int. Ed. 53, 5868-5871 (2014) *-SSO Type material: SSZ-61 Smeets, S., Xie, D., Baerlocher, Ch., McCusker, L.B., Wan, W., Zou, X. and Zones, S.I. "High-Silica Zeolite SSZ-61 with Dumbbell-Shaped Extra-Large-Pore Channels" Angew. Chem. Int. Ed. 53, 10398-10402 (2014) UOV Type material: IM-17 Lorgouilloux, Y., Dodin, M., Mugnaioli, E., Marichal, C., Caullet, P., Bats, N., Kolb, U. and Paillaud, J.-L. "IM-17: a new zeolitic material, synthesis and structure elucidation from electron diffraction ADT data and Rietveld analysis" RSC Adv. 4, 19440-19449 (2014)

三联吡啶的合成及其金属配合物研究进展

三联吡啶的合成及其金属配合物研究进展1刖言配位化学早期是在无机化学基础上发展起来的一门边沿学科，如今，配位化学在有机化学与无机化学的交叉领域受到化学家门广泛的关注。

有机-金属配合物在气体分离、选择性催化、药物运输和生物成像等方面都有潜在的应用前景，因此日益成为化学研究的热点领域［1-4］。

多联吡啶金属配合物在现代配位化学中占据着不可或缺的位置，常见的多联吡啶配体包括2,2'-二联吡啶（bpy ）和2,2':6'2'-三联吡啶（tpy ）（Fig. 1），Hosseini 就把bpy 称为“最广泛应用的配体” ［5］，与其类似的具有三配位点的tpy 的合成及其金属配合物的研究同样是化学家们研究的热点［6-8］。

Fig 1.三联吡啶的三个吡啶环形成一个大的共轭体系，具有很强的（7给电子能力，配合物中存在金属到配体的d 一 n *反馈成键作用，因而能与大多数金属离子均形成稳定结构的配合物。

然而，三联吡啶金属络合物的特殊的氧化还原和光物理性质受其取代基电子效应的影响。

因此，通过引入不同的取代基，三联吡啶金属络合物可用于荧光发光装置以及光电开关等光化学领域［9-10］。

在临床医学和生物化学领域中，不管是有色金属的测定还是作为DNA 的螯合试剂，三联吡啶衍生物都具有非常广泛的应用前景［11-12］。

2三联吡啶的合成研究进展正因为三联吡啶在许多领域都具有潜在的应用价值，所以对其合成方法的研究十分重要。

三联吡啶的合成由来已久，早在 1932年，Morgan 就首次用吡啶在FeCR 存在下反应合成分离出了三联吡啶，并发现了三联吡啶与Fe （ II ）的配合物［13］。

目前，合成三联吡啶terpyridine tpy的方法主要有成环法和交叉偶联法两种。

2.1成环法成环法中最常用的反应是Kr? hnke 缩合反应( Scheme 1)[14]，首先2-乙酰基吡啶溴化得到化合物2, 2与吡啶反应生成吡啶溴盐3, 3与a 3■不饱和酮4进行Michael加成反应得到二酮5，在醋酸铵存在下进而关环得到三联吡啶。

配位化学综述

This article was downloaded by: [Lanzhou University]On: 16 March 2015, At: 07:10Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UKClick for updatesJournal of Coordination ChemistryPublication details, including instructions for authors and subscription information:/loi/gcoo20Design, synthesis and structure ofuranyl coordination polymers from 2-D layer to 3-D network structureSi Yue Wei a, Feng Ying Bai b, Ya Nan Hou a, Xiao Xi Zhang a, Xue Ting Xu a, Ji Xiao Wang a, Huan Zhi Zhang c& Yong Heng XingaaCollege of Chemistry and Chemical Engineering, Liaoning Normal University , Dalian, PR ChinabCollege of Life Sciences, Liaoning Normal University , Dalian, PR ChinacGuangxi Key Laboratory of Information Materials, Guilin University of Electronic T echnology , Guilin, PR ChinaAccepted author version posted online: 27 Nov 2014.Published online: 02 Jan 2015.PLEASE SCROLL DOWN FOR ARTICLETaylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However , Taylor & Francis,our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims,proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content.This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015Design,synthesis and structure of uranyl coordination polymers from 2-D layer to 3-D network structureSI YUE WEI †,FENG YING BAI ‡,YA NAN HOU †,XIAO XI ZHANG †,XUE TING XU †,JI XIAO WANG †,HUAN ZHI ZHANG §and YONG HENG XING *††College of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian,PR China‡College of Life Sciences,Liaoning Normal University,Dalian,PR China§Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology,Guilin,PR China(Received 7January 2014;accepted 8October 2014)Solvothermal reaction of uranyl acetate and succinic acid in DMF resulted in formation of three uranyl coordination polymers,[(UO 2)4(μ2-OH)7(OH)6]·2(H 2O)·(H 3O)·4NH 2(CH 3)2(1),[(UO 2)(μ2-OH)(OH)3]·2NH 2(CH 3)2](2),and [(DMF)2(UO 2)(μ2-OH)4(UO 2))](3).The products were characterized by elemental analysis,IR spectroscopy,X-ray single crystal,and powder diffraction.Structural analysis shows that 1is a layer,2and 3are 3-D network structures.Keywords :Coordination polymer;Solvothermal reaction;Crystal structure;DMF hydrolysis1.IntroductionUranyl compounds have attracted attention for potential applications in ion exchange [1,2],proton conductivity [3],photochemistry [4,5],nonlinear optical materials [6,7],catalysis [8],and especially in energy and the military.The directed assembly of discrete molecules to build polymeric arrays is a topic of interest,and crystal engineering provides a tool for realization of such targets.The predictable self-assembly of low-dimensional molecules into high-dimensional frameworks through weak intermolecular interactions such as hydrogen bonds,weak van der Waals interactions,and π–πstacking is an important strategy in crystal*Corresponding author.Email:xingyongheng@ ©2014Taylor &FrancisJournal of Coordination Chemistry ,2015V ol.68,No.3,507–519,/10.1080/00958972.2014.992341D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015engineering [9].Oxygen and nitrogen-containing organic compounds are often used to construct diverse structures and functional uranyl compounds,providing the possibility of forming hydrogen-bonded network structures.In some cases,hydrogen bonds link uranyl discrete clusters to form chains,layers,or even 3-D network structures.Design,synthesis,and structures of uranyl compounds composed of uranyl carboxylates such as [UO 2)3(Hcit)2(H 2O)3]·2H 2O [10],uranyl phosphonates and carboxyphosphonates such as Co 2[(UO 2)6(PO 3CH 2CO 2)6(H 2O)13]·6H 2O [11],and uranyl curbit[n]urils such as [UO 2(CB 5)](ReO 4)2·2H 2O and [s 2(CB 5)(H 2O)2][(UO 2)2(HCOO)(OH)4]2·3H 2O [12]have been described.However,studies of uranyl coordination polymers with solvents as ligands are rare.The UO 22þspecies with inactive U=O double bonds generally is coordinated only through equatorial ligands,yielding in ﬁnite chains or sheets,while 3-D framework struc-tures are formed occasionally .In this work,three uranyl coordination polymers have beensynthesized.We employ a common ligand (DMF)to connect UO 2þ2to form uranyl poly-mers from 2-D layer to 3-D network structures.DMF can be used as a solvent and a coordi-nated ligand.DMF is easily hydrolyzed,producing NH 2(CH 3)2+in strong acid,strong base,or high temperature [13].In this paper,we use these properties of DMF hydrolysis and coordination to construct three uranyl coordination polymers,[(UO 2)4(μ2-OH)7(OH)6]·2(H 2O)·(H 3O)·4NH 2(CH 3)2(1),[(UO 2)(μ2-OH)(OH)3]·2NH 2(CH 3)2](2),and [(DMF)2(UO 2)(μ2-OH)4(UO 2))](3).2.Experimental2.1.Materials and methodsIR spectra were recorded on a JASCO FT/IR-480PLUS Fourier transform spectrometer with pressed KBr pellets from 200to 4000cm –1and a Bruker AXS TENSOR −27FTIR spectrometer with KBr pellets from 4000to 400cm −1.Elemental analyses for C,H,and N were carried out on a PerkinElmer 240C automatic analyzer.X-ray powder diffraction (PXRD)patterns were obtained on a Bruker Avance-D8equipped with Cu K αradiation (λ=1.54183Å),in the range 5°<2θ<50°,with a stepsize of 0.02°(2θ)and a count time of 2s per step.2.2.SynthesisAll chemicals purchased were of reagent grade or better and used without puri ﬁcation.Caution !While the uranium compound used in these studies contained depleted uranium,precautions are needed for handling radioactive materials,and all studies should be conducted in a laboratory dedicated to studies of radioactive materials.2.2.1.Synthesis of [(UO 2)4(μ2-OH)7(OH)6]·2(H 2O)·(H 3O)·4NH 2(CH 3)2(1).A mixture of UO 2(CH 3COO)2·2H 2O (0.0326g,0.0769mM)and succinic acid (0.0290g,0.25mM)in DMF (4mL)was stirred for 1h at room temperature,then the pH adjusted to 7by solu-tion of sodium hydroxide (1M).The mixture was introduced into a reaction kettle and heated statically at 160°C for three days.Resulting light yellow product was then ﬁltered508S.Y.Wei et al.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015off,washed with water,and dried in air.Anal.Calcd for C 8H 52N 4O 24U 4(%):C,6.23;H,3.36;and N,3.64.Found (%):C,6.20;H,3.29;and N,3.69.2.2.2.Synthesis of [(UO 2)(μ2-OH)(OH)3]·2NH 2(CH 3)2](2).The preparation is similar to that of 1except that the temperature was changed to 100°C and pH adjusted to 2by solution of nitric acid (1M).Yellow crystals of 2were obtained after washing by water several times.Anal.Calcd for C 4H 20N 2O 6U (%):C,11.2;H,4.65;and N,6.51.Found (%):C,11.0;H,4.61;and N,6.42.2.2.3.Synthesis of [(DMF)2(UO 2)(μ2-OH)4(UO 2))](3).The preparation is similar to that of 1except that the temperature was changed to 80°C.Yellow crystals of 3were obtained after washing by water several times.Anal.Calcd for C 6H 18N 2O 10U 2(%):C,9.55;H,2.39;and N,3.71.Found (%):C,9.44;H,1.94;and N,3.60.2.3.X-ray crystallographic determinationA single crystal with dimensions 0.58mm ×0.34mm ×0.18mm for 1was selected for structure determination.Re ﬂection data were collected at room temperature on a Bruker AXS SMART APEX II CCD diffractometer with graphite monochromated Mo-K αradiation (λ=0.71073Å)from 1.87<θ<25.00°.A total of 20,048(4303unique,R int =0.0456)re ﬂections were measured.The structure of 2was determined by single crystal X-ray dif-fraction.A yellow single crystal of 2with dimensions 0.50mm ×0.34mm ×0.18mm was mounted on a glass ﬁber.Re ﬂection data were collected at room temperature on a Bruker AXS SMART APEX II CCD diffractometer with graphite monochromated Mo-K αradiation (λ=0.71073Å)from 2.17<θ<25.00°.A total of 4612(1941unique,R int =0.0575)re ﬂec-tions were measured.In 2,the largest diff.peak and hole are 7.418and −4.975e Å–3and the major residual peaks appear around U (U1–Q1and U1–Q2bond lengths are 0.883and 0.902Å).The structure of 3was determined by single crystal X-ray diffraction.A yellow single crystal of 3with dimensions 0.44mm ×0.38mm ×0.13mm was mounted on a glass ﬁber.Re ﬂection data were collected at room temperature on a Bruker AXS SMART APEX II CCD diffractometer with graphite monochromated Mo-K αradiation (λ=0.71073Å)from 2.17<θ<25.00°.A total of 9043(3637unique,R int =0.0362)re ﬂections were measured.In 3,the largest diff.peak and hole are 7.133and −1.398e Å–3and the major peaks appear around U (U1–Q1and U2–Q2bond lengths are 0.829and 0.811Å).Empirical absorption corrections were applied using multi-scan technique.All absorption corrections were per-formed using SADABS [14].Crystal structures were solved by direct methods.All nonhy-drogen atoms were re ﬁned with anisotropic thermal parameters by full-matrix least-squares calculations on F 2using SHELXL-97[15].Hydrogens on carbon and nitrogen were ﬁxed at calculated positions and re ﬁned using a riding model,but the hydrogens of lattice water molecule in 1were found in the difference Fourier map.The hydrogens of the μ2-O (O3,O5,O6,O10for 1;O3for 2;O3,O4,O5,O8for 3)and the U –Ot from terminal hydroxo ions (O4,O9,O14for 1;O4,O5,O6for 2)were not located.Crystal data and details of the data collection and the structure re ﬁnement are given in table 1.Selected bond distances and angles are given in table 2.Figures and drawings were made with Diamond 3.2.Uranyl coordination polymers 509D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 20153.Results and discussion 3.1.SynthesisUO 2(CH 3COO)2·2H 2O and succinic acid were used as starting materials while a solvother-mal synthesis assisted by DMF was adopted to prepare the uranyl complexes.Originally,we added succinic acid to the system to obtain a uranium coordination polymer with car-boxylic acids [16],unfortunately,reaction results show that the succinic acid is not coordi-nated with uranyl,and protonated NH 2(CH 3)2+cation,which is produced by DMF hydrolysis that connects with uranyl by hydrogen bonds or DMF directly coordinated with uranyl.When succinic acid was not added in the synthetic system,we do not obtain 1–3.Thus,the addition of the succinic acid is necessary in the reaction.In the reactions,simi-larly,pH is also essential to the polymerization of uranyl.Isolated UO 22þcations exist in aqueous solution (pH <2.5).However,in less acidic media,the identity of uranyl species varies with the concentration of OH −(aq)ions [17].When pH >2.5,UO 22þtends to hydro-lyze and polymerize,forming a number of polynuclear uranyl species,and then generate complex precipitates,such as U 2O 52þand U 3O 82þ[17].The main factors which in ﬂuencethe hydrolysis are temperature and the concentration of UO 22þ.The process of UO 2þ2hydrolysis is shown below:Table 1.Crystal data of 1–3.Complexes123FormulaC 8H 52N 4O 24U 4C 4H 20N 2O 6U C 6H 18N 2O 10U 2Formula weight 1540.66430.25754.28Crystal system Orthorhombic Monoclinic Monoclinic Space group PnmaC2/cC2/ca (Å)17.0296(13)13.620(4)23.848(2)b (Å)22.1116(17)8.709(2)7.3947(7)c (Å)9.0134(7)19.604(5)17.0358(16)α(°)909090β(°)90100.957(4)97.690(2)γ(°)909090V (Å3)3394.0(5)2283.0(10)2977.3(5)Z488D Calcd (g cm −3) 3.0152.5033.366Crystal size/mm 0.58×0.34×0.180.50×0.34×0.180.44×0.38×0.13F (000)275215842656μ(Mo-K α)/mm −119.11414.22421.777θ(°)1.84–28.342.79–24.99 1.72–28.37Re ﬂections collected20,04846129043Independent re ﬂections [I >2σ(I )]4303(3615)1941(1687)3637(2856)Parameters 198123185Goodness of ﬁt 1.0301.11.045R a 0.0427(0.0535)b 0.0877(0.0950)b 0.0390(0.0565)b wR 2a0.1079(0.1134)b0.2461(0.2546)b0.0948(0.1021)ba R =ΣêêF o ê−êF c êê/ΣêF o ê,wR 2={Σ[w (F o 2−F c 2)2]/Σ[w (F o 2)2]}1/2;[F o >4σ(F o )].bBased on all data.510S.Y.Wei et al.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015Under highly acidic conditions,the monomeric UO 22þcation directly takes part in crystal growth (such as 2).A binuclear model of uranyl complex was composed under pH 7and solvothermal conditions,and the binuclear species with uranium coordination to DMF (such as 3).For trinuclear (UO 2)3(μ2-OH)5+,the species may lose a water to form a oxo-hydroxo-uranium polyhedral cation,(UO 2)3O(μ2-OH)3+[18].In the relatively high pH values,oligomeric uranyl species are formed and subsequently involved in crystallization of uranyl complex.3.2.Crystal structure analysis3.2.1.Crystal structure of plex 1crystallizes in the orthorhombic system with Pnma space group.Selected bond distances and angles of 1are given in table 2.X-ray single crystal analysis indicates that the asymmetric unit of 1is made up of two UO 22þTable 2.Selected bond distances (Ǻ)and angles (°)for 1–3.*Complex 1O(1)–U(1) 1.774(7)O(2)–U(1) 1.767(7)O(3)–U(1) 2.298(5)O(4)–U(1) 2.251(5)O(6)–U(1) 2.289(5)O(7)–U(2) 1.767(9)O(8)–U(2) 1.772(9)O(9)–U(2) 2.258(5)O(10)–U(2) 2.296(7)O(11)–U(3) 1.774(9)O(12)–U(3) 1.769(9)O(10)–U(3) 2.313(7)O(13)–U(3) 2.256(5)U(1)–O(3)–U(2)157.1(2)U(1)–O(6)–U(3)161.4(3)U(2)–O(10)–U(3)146.9(4)O(2)–U(1)–O(1)178.3(4)O(1)–U(1)–O(6)90.3(3)O(4)–U(1)–O(3)76.17(19)O(2)–U(1)–O(4)91.1(3)O(2)–U(1)–O(6)90.3(3)O(4)–U(1)–O(6)154.87(19)O(2)–U(1)–O(5)89.7(3)O(7)–U(2)–O(9)#290.8(3)O(7)–U(2)–O(8)178.7(4)O(8)–U(2)–O(9)90.3(3)O(8)–U(2)–O(10)89.8(4)O(9)–U(2)–O(10)143.38(14)O(12)–U(3)–O(11)179.1(4)O(11)–U(3)–O(13)#291.2(3)O(13)–U(3)–O(10)141.76(14)O(11)–U(3)–O(13)91.2(3)O(12)–U(3)–O(10)88.1(4)O(10)–U(3)–O(6)68.98(13)Complex 2U(1)–O(1) 1.793(13)U(1)–O(2) 1.792(12)U(1)–O(4) 2.235(12)U(1)–O(3)2.364(11)U(1)–O(5)2.244(11)U(1)–O(6)2.323(10)O(1)–U(1)–O(2)177.3(7)O(2)–U(1)–O(4)92.4(6)O(4)–U(1)–O(5)77.7(5)O(4)–U(1)–O(6)151.5(5)O(1)–U(1)–O(3)90.5(6)U(1)–O(3)–U(1)#1115.5(4)O(5)–U(1)–U(1)#1178.2(4)O(6)–U(1)–O(3)#1136.8(4)O(1)–U(1)–O(4)92.4(6)O(2)–U(1)–O(5)89.7(7)O(5)–U(1)–O(6)73.9(4)O(4)–U(1)–O(3)136.1(5)O(5)–U(1)–O(3)146.1(4)O(6)–U(1)–O(3)72.3(4)O(5)–U(1)–U(1)#1178.2(4)Complex 3U(1)–O(1) 1.747(7)U(1)–O(2) 1.755(8)U(1)–O(4) 2.290(6)U(1)–O(3) 2.324(6)U(1)–O(5)#1 2.325(5)U(1)–O(5) 2.327(5)U(1)–O(3)#2 2.332(5)U(1)–U(1)#1 3.9199(4)U(1)–U(1)#2 3.9199(4)U(2)–O(6) 1.746(7)U(2)–O(7) 1.752(7)U(2)–O(4) 2.291(6)U(2)–O(8) 2.323(6)U(2)–O(8)#3 2.331(6)U(2)–O(10) 2.377(7)U(2)–O(9)2.382(8)U(1)–U(1)#23.9199(4)U(2)–U(2)#33.8961(8)O(1)–U(1)–O(2)179.2(4)O(1)–U(1)–O(4)87.8(3)O(2)–U(1)–O(4)91.5(3)O(1)–U(1)–O(3)92.6(3)O(1)–U(1)–O(5)#189.1(3)O(4)–U(1)–O(5)#1140.9(2)O(1)–U(1)–O(5)90.4(3)O(4)–U(1)–O(5)77.7(2)O(2)–U(1)–O(3)#290.7(3)O(3)–U(1)–O(3)#2141.33(15)O(4)–U(1)–U(1)#2109.96(16)O(3)–U(1)–U(1)#2173.89(13)O(8)–U(2)–U(2)#333.24(15)O(10)–U(2)–U(2)#3104.07(19)O(6)–U(2)–O(7)178.7(4)O(6)–U(2)–O(4)91.2(3)O(7)–U(2)–O(4)89.7(3)O(6)–U(2)–O(8)90.4(3)O(7)–U(2)–O(8)88.3(3)O(4)–U(2)–O(8)138.6(2)O(6)–U(2)–O(10)88.2(3)O(7)–U(2)–O(10)91.5(3)O(4)–U(2)–O(10)150.5(2)O(8)–U(2)–O(10)70.9(2)O(6)–U(2)–O(9)91.5(3)O(7)–U(2)–O(9)89.6(3)O(8)–U(2)–O(9)145.7(3)*Symmetry codes:#1:−x ,1−y ,2−z ;#2:x ,1.5−y ,z for 1;#1:1.5−x ,0.5−y ,1−z for 2;#1:−x +y ,0.5−y ,1−z ;#2:0.5−x ,0.5+y ,0.5−z ;#3:0.5−x ,−0.5+y ,0.5−z for 3.Uranyl coordination polymers511D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015cations,three and a half hydroxo bridge groups,three terminal hydroxo ions,two free protonated NH 2(CH 3)2+cations,a free water,and a half protonated water (H 3O +).O1W is protonated water and O2W is water molecule.From the coordination environment of U (ﬁgure 1),the three uranium ions are all seven-coordinate.The U1center is coordinated with seven oxygens (O1,O2,O3,O4,O5,O5#2,and O6;#2:−x ,1−y ,1−z )to form a pentagonal bipyramid geometry,O1and O2are terminal oxygens,O4is from terminal hydroxo ions,and O3,O5,O5#2(#2:−x ,1−y ,1−z ),and O6are hydroxo bridge atoms.Through hydroxo bridge atoms (O3and O6),U1is further connected with U2and U3,respectively.U2and U3are connected by hydroxo bridge (O10).U1,U2,U3,O3,O6,and O10are self-assembled to form a twisty six-member ring.U2is bonded with seven oxygens (O3,O7,O8,O9,O10,O3#1,O9#1,#1:x ,1.5−y ,z )with O7and O8terminal,O9and O9#1are from terminal hydroxo ions,and O3and O3#1(#1:x ,1.5−y ,z )are hydroxo bridges to generate a pentagonal bipyramid geometry.The coordination environments of U2and U3are quite similar,except that the pair of terminal hydroxo groups on each U center (adjacent in the pentagonal plane)is different.The O9⋯O9#1separation on U2is 2.69Å,whereas the corresponding separation between terminal hydroxo groups onU3Figure 1.The coordination environment of U in 1(hydrogens omitted for clarity).Symmetry codes:#1:−x ,1−y ,2−z ;#2:x ,1.5−y ,z.Figure 2.A 1-D chain network structure of 1.512S.Y.Wei et al.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015(O13···O13#1)is 2.79Å.The U=O bond lengths range from 1.756(10)to 1.789(12)Å,the bond lengths of U –O t from terminal hydroxo ions vary from 2.251(5)to 2.258(5)Å,and the bond lengths of U –O b from hydroxo bridges vary from 2.248(5)to 2.385(5)Å.The average bond length of U –O b is 2.325(5)Åwhich matches that of 2.33(3)Åfrom the CSD,and is close to that reported [19](2.35(4)Å),but is much shorter than the corresponding bond length of U –O W from coordination water (2.406Å)[20].The bond angles of O=U=O range from 178.0(6)to 179.6(6)°and the bond angles of O –U –O vary from 63.9(3)to 157.0(4)°.In the packing of 1,four adjacent O=U=O are connected by hydroxo bridges to form a building block of (UO 2)4(μ2-OH)9(OH)4.These two adjacent building blocks further share two hydroxo bridges and expanded along the b axis to form a 1-D chain.There are strong H-bonds between the protons on nitrogen of the dimethylammonium cations and oxygen of the chain (ﬁgure 2).The hydrogen bonds are N2–H2D ⋯O13, 2.7244Å,167.00°;N2–H2E ⋯O4,2.8667Å,148.00°;N2–H2E ⋯O5,2.7943Å,133.00°,while H2E is the hydrogen of a bifurcated hydrogen bond.Furthermore,the chain is more stable in the pres-ence of these hydrogen bonds.Adjacent chains are further connected by C3–H3B ⋯O1(3.2531Å,140.00°)to form a 2-D layer structure (ﬁgure 3).3.2.2.Crystal structure of plex 2crystallizes in the monoclinic system with C2/c space group.Selected bond distances and angles of 2are given in table 2.X-ray single crystal analysis indicates that 2is made up of one crystallographically independent UO 22þ,one hydroxo bridge,three terminal hydroxo ions,and two protonated NH 2(CH 3)2+cations.Figure 3.A view of hydrogen-bonding interactions of 1.Uranyl coordination polymers 513D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015U(VI)is seven-coordinate (ﬁgure 4),O1and O2are terminal oxos,O4,O5,and O6originate from terminal hydroxo ions,and O3and O3#1(#1: 1.5−x ,0.5−y ,1−z )are hydroxo bridges in a pentagonal bipyramid.The U=O bond lengths range from 1.792(13)to 1.793(13)Å.The bond lengths of U –O t from terminal hydroxo ions vary from 2.235(12)to 2.323(10)Åand the bond lengths of U –O b from bridging hydroxo groups range from 2.235(12)to 2.383(11)Å.The average U –O b bond length is 2.374(11)Å,matching that of 2.33(3)Åfrom the CSD,and close to that reported [19](2.35(4)Å),but shorter than the bond length of U –O W (2.406Å)reported [20].The bond angle of O=U=O is 177.3(7)°and the bond angles of O –U –O vary from 64.5(4)to 151.5(5)°.In the molecular packing,a cluster unit [(UO 2)2(μ2-OH)2(OH)6]is connected by two types of hydrogen bonds,N –H ⋯O and C –H ⋯O.They are N1–H1NA ⋯O5,N1–H1NB ⋯O6,N2–H2NA ⋯O3,N2–H2NA ⋯O4,N2–H2NB ⋯O6,and C3–H3B ⋯O6.The hydrogen bond connecting mode is illustrated in ﬁgure 5.Two adjacent cluster units [(UO 2)2(μ2-OH)2(OH)6]are connected by hydrogen bonds (N2–H2NA ⋯O4, 2.9698Å,139.58°;N2–H2NB ⋯O6,2.7317Å,169.98°)and expanded to form an in ﬁnite chain along the b axis.Adjacent chains are further connected by the cluster units with intermolecular hydrogen bonds (N1–H1NA ⋯O5,2.5820Å,169.95°;N1–H1NB ⋯O6,2.7679Å,169.34°)to form a 3-D network structure (ﬁgure 6).3.2.3.Crystal structure of plex 3crystallizes in the monoclinic system with C2/c space group.Selected bond distances and angles of 3are given in table 2.X-ray single crystal analysis indicates that 3is made up of two UO 22þcations,four hydroxo bridges,and two DMF molecules.U1and U2are seven-coordinate.The two distinct uranyl ions,U1and U2,have nearly linear [O=U=O]2+bond angles of 179.3(4)and 178.7(4)°,respec-tively.U1(VI)is coordinated by O1and O2(U(1)–O(1),1.748(7)Å;U(1)–O(2),1.755(8)Å)from terminal oxo groups,O3,O3#3,O4,O5,and O5#2(#2:0.5−x ,0.5+y ,0.5−z ;#3:0.5−x ,−0.5+y ,0.5−z )from hydroxo bridges to form a pentagonal bipyramid.Similarly,U2(VI)is coordinated by O6and O7(U(2)–O(6),1.749(7)Å;U(2)–O(7),1.751(7)Å)from terminal oxos,O8and O8#1(#1:−x ,y ,0.5−z )from hydroxo bridges,and O9and O10from DMF (U(2)–O(9), 2.382(8)Å;U(2)–O(10), 2.377(7)Å)to form apentagonalFigure 4.The coordination environment of U in 2(hydrogens omitted for clarity).Symmetry codes:#1:1.5−x ,0.5−y ,1−z .514S.Y.Wei et al.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015bipyramid (ﬁgure 7).The average bond length of U –O DMF is 2.380(8)Å,close to 2.401(4)Åreported [16].Bond lengths of U –O b from bridging hydroxo groups vary from 2.290(6)to 2.332(5)Åand bond angles O −U −O vary from 119.0(10)to121.4(10)°.Figure 5.Hydrogen bonds connecting of 2.Figure 6.A view of hydrogen-bonding interactions of 2.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015There is a hydrogen bond based on C –H ⋯O in the framework structure,including C3–H3B ⋯O1,C6–H6A ⋯O3,and C6–H6C ⋯O7.Two adjacent units UO 2(μ2-OH))are con-nected by two hydroxo bridges and expanded along the b axis to form a 1-D chain.Parallel chains are further bridged by building blocks of [(OH)(DMF)2(UO 2)(OH)2(UO 2)(DMF)2(OH)]to form a 2-D network structure with the coordinated DMF oriented above and below the mean plane of the network (ﬁgure 8).The 2-D network structure is further connected by hydrogen bonds (C3–H3B ⋯O1,3.3869Å,170.86°;C6–H6A ⋯O3,3.2948Å,144.60°;C6–H6C ⋯O7,3.2677Å,138.78°)to form a 3-D network structure (ﬁgure 9).3.3.IR spectroscopyIn IR spectra [ﬁgure S1(a)–(c),see online supplemental material at /10.1080/00958972.2014.992341]of the complexes,the broad absorptions at 3456,3376,and 3442cm −1indicate the presence of N –H stretching of DMF.The bands at 2920,2912,and 2943cm −1are attributed to the presence of asymmetrical C –H (CH 3)stretches.The bands at 1642,1633,and 1655cm −1are attributed to bending of N –H.The bands at 1469–1363cm −1are assigned to C –H bending.Bands at 918,929,and 923cm −1are assigned to the U=O stretch.The FTIR spectra of the complexes are consistent with the structural analyses;detailed assignment of the IR spectra for 1–3is shown in table 3.3.4.X-ray powder diffraction studyThe simulated and experimental PXRD spectra of 1–3are shown in Supplementary material (ﬁgures S2–S4).The experimental PXRD spectra accord with the simulated PXRD spectrum,indicating that 1–3are pure phase,withoutimpurities.Figure 7.The coordination environment of U in 3(hydrogens omitted for clarity).Symmetry codes:#1:−x +y ,0.5−y ,1−z ;#2:0.5−x ,0.5+y ,0.5−z ;#3:0.5−x ,−0.5+y ,0.5−z .D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015Figure 8.A 2-D layer network structure of 3viewed from the a –bplane.Figure 9.A view of hydrogen-bonding interactions of 3.D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 20154.ConclusionWe have reported three uranyl complexes,[(UO 2)4(μ2-OH)7(OH)6]·2(H 2O)·(H 3O)·4NH 2(CH 3)2(1),[(UO 2)(μ2-OH)(OH)3]·2NH 2(CH 3)2](2),and [(DMF)2(UO 2)(μ2-OH)4(UO 2))](3).For 1,the building block ((UO 2)4(μ2-OH)9(OH)4)is shared by two hydroxo bridges and further expanded along the b axis to form a 1-D chain;adjacent chains are further connected by hydrogen bonds (N –H ⋯O and C –H ⋯O)to form a 2-D layer.For 2,[(UO 2)2(μ2-OH)2(OH)6]is connected by hydrogen bonds (N –H ⋯O and C –H ⋯O)to form a 3-D network structure.For 3,DMF is monodentate and connected by hydrogen bonds (C –H ⋯O)to form a 3-D network structure.Research is in progress with the aim of exploring the uranium coordination chemistry with different ligands and further study of their properties.Supplementary materialTables of atomic coordinates,isotropic thermal parameters,and complete bond distances and angles have been deposited with the Cambridge Crystallographic Data Center.Copies of this information may be obtained free of charge by quoting the publication citation and deposition numbers CCDC for 1–3:979412,979413and 979414,respectively,from the Director,CCDC,12Union Road,Cambridge,CB21EZ,UK (Fax:+441223336033;Email:deposit@ or ).AcknowledgementsWe thank Natural Science Foundation of China [grant number 21371086]and Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology,PR China (Project No.1210908-06-K)for ﬁnancial assistance.References[1]P.O.Adelani,T.E.Albrecht-Schmitt.Angew.Chem.,Int.Ed.,49,8909(2010).[2]P.O.Adelani,T.E.Albrecht-Schmitt.Inorg.Chem.,50,12184(2011).[3]D.Grohol,M.A.Subramania,D.M.Poojary,A.Clear ﬁeld.Inorg.Chem.,35,5264(1996).[4]K.E.Knope,C.L.Cahill.Inorg.Chem.,48,6845(2009).[5]Y .S.Jiang,Z.T.Yu,Z.L.Liao,G.H.Li,J.S.Chen.Polyhedron ,25,1359(2006).[6]K.M.Ok,J.Baek,P.S.Halasyamani,D.O ’Hare.Inorg.Chem.,45,10207(2006).[7]S.Wang,E.V .Alekseev,J.Ling,G.Liu,W.Depmeier,T.E.Albrecht-Schmitt.Chem.Mater.,22,2155(2010).[8]Z.L.Liao,G.D.Li,M.H.Bi,J.S.Chen.Inorg.Chem.,47,4844(2008).Table 3.IR spectra of 1–3.Complexes 123νNH 345633763442ν(CH3)292029122943δNH 164216331655δC –H 1469,139614011435,1363νU=O918929923D o w n l o a d e d b y [L a n z h o u U n i v e r s i t y ] a t 07:10 16 M a r c h 2015。

金属原子簇化学

Aprotic Synthesis and Structural Determination of the Nanosized 6- Hexaanion Nonprotonated 3-Octahedral [Pt6Ni38(CO)48] Stabilized as a Cubic Solvated [NMe4]+ Salt Namal de Silva and Lawrence F. Dahl IC 2006 pp 8814 - 8816
CO CO CO
CO
例
推测Co4(CO)12的可能结构 9 4 + 2 12 = 60 每个中心Co的平均外层电子数 = 60/4 = 15 每个Co缺3个电子必定形成3个Co-Co键
理想结构为：
OC OC OC Co CO Co CO CO
测定结构为：
OC OC
Co
Co OC
CO CO
CO
p M L
M L
1、羰基化合物的合成与性质
合成
1）直接反应法
Ni＋4CO Fe+5CO
Ni(CO)4 Fe(CO)5
1890年第一个 200℃ 200 atm V(CO)6 Cr(CO)6
2）还原法
VCl3 + Na +CO CrCl3 + RMgX + CO
反应 1) 简单取代
Re2O7 + CO
Comparative Bonding Behavior of Functional Cyclopentadienyl Ligands and Boron-Containing Analogues in Heterometallic Complexes and Clusters P. Croizat, N. Auvray, P. Braunstein, R. Welter IC 2006 pp 5852 - 5866

金属有机化学论文

金属有机化学中卡宾的发展摘要在过渡金属有机化学中, 含过渡金属-主族元素(C, N, P)双键的卡宾配合物化学具有重要地位. 它不仅对人们理解过渡金属和主族元素的成键理论很重要, 而且这类配合物具有一些很好的、以及特征性的反应和催化性能. 在过去的30 年中, 人们在含稀土金属-主族元素(C, N, P)单键的稀土金属烷基、胺基配合物以及膦基配合物化学研究上取得了很好的进展. 稀土卡宾配合物化学是相关研究工作者接下来需要和渴望开拓的一个重要领域. 人们在这一方面进行了积极的探索,合成得到了一些稀土桥联卡宾配合物和稀土卡宾配合物的模拟物. 虽然它们离稀土金属----主族元素双键的稀土末端卡宾配合物有差距, 但可以为稀土末端卡宾配合物的研究提供一些线索. 本论文论述了这方面的研究成果, 以及最近在稀土末端氮卡宾配合物上的一个突破.关键词稀土碳卡宾氮卡宾膦卡宾合成反应性能稀土元素是由处于Ⅲ B族的钪、钇及镧系金属 , 共 17种元素组成. 稀土元素独特的电子层结构, 决定了它们具有不同于主族和其他过渡金属元素的独特化学性质. 与主族金属相比, 稀土金属离子配位数高, 更有利于底物的络合和活化 . 与其他过渡金属相比, 稀土金属离子和配体之间的配位没有方向性 , 在空间允许的条件下趋向于高配位; 大部分稀土金属离子具有+3价的稳定价态(Ce, Eu, Yb, Sm离子相对容易变价 ), 不易发生 d区过渡金属配合物中常见的氧化加成和还原消除反应 ; 稀土元素虽然属于副族 , 但稀土金属 -碳键和稀土金属 -氮键的离子性强 , 具有很好的反应活性 ; 由于氧化态较高 , 从软硬酸碱分类上看, 稀土金属离子属于硬酸, 易于与 O和 N等硬碱配体作用, 具有强的亲氧、亲氮性, 而与在 d区过渡金属配合物中广泛应用的软碱配体, 如有机膦、烯烃及羰基等作用较弱, 一般难以形成稳定的配合物.在过去的 30年中, 人们对含稀土金属-主族元素 (C, N, P)单键的稀土金属烷基、胺基以及膦基配合物已经有了广泛的探索和研究 . 这些配合物表现出丰富多样的结构特征和反应性能, 已经被用于催化有机合成和聚合物合成. 然而, 在合成含稀土金属-主族元素 (C, N, P)双键的稀土金属末端碳卡宾、氮卡宾和膦卡宾配合物方面仍面临挑战. 在过渡金属有机化学中 , 卡宾配合物化学具有重要地位 .它不仅对人们理解过渡金属和主族元素的成键理论很重要, 而且这类配合物具有一些很好的、以及特征性的反应和催化性能. 如其涉及烯烃复分解反应,环丙烷化,Fischer-Tropsch 合成, 与烯烃和炔烃的环金属化, 氢胺化反应, 磷氢化反应, 碳氢键活化和其他许多有机官能团的转换反应等.含稀土金属-主族元素(C, N, P)双键的稀土金属末端卡宾配合物难于合成的一个主要原因在于硬酸性的稀土金属离子和卡宾基团的轨道能量匹配性差[12]. 另外, 稀土金属离子的大离子半径和高配位数的特征, 也使得稀土金属末端卡宾配合物易于发生聚集, 卡宾基团以桥联的形式存在, 从而失去稀土金属-主族元素双键结构和反应特性. 稀土金属末端卡宾配合物化学是稀土金属有机化学领域最具挑战性的课题之一, 人们在这一方面进行了很多尝试. 本文论述了人们在这方面的探索过程和结果. 文中介绍含二价阴离子(CR22−,NR2−, PR2−)卡宾基团的稀土配合物, 对于中性氮杂环卡宾, 因为其特性和二价阴离子卡宾基团有本质差别, 在此不作论述.一、稀土卡宾配合物1.稀土碳卡宾配合物1979 年, Schumann 等报道了离子对型的稀土烷基配合物[Li(Et2O)4][Lu(CH2SiMe3)4]会慢慢分解, 脱去SiMe4, 生成一个新的配合物, 这个配合物在元素分析结果上符合稀土卡宾配合物Li[Lu(CH2SiMe3)2-(CHSiMe3)]的组成. 将该配合物与TMEDA(四甲基乙二胺) 反应, 他们得到了[Li(TMEDA)] [Lu-(CH2SiMe3)2(CHSiMe3)], 并通过1H NMR、元素分析、红外光谱以及熔点测定对其进行了表征. 另外, 通过[Er(CH2SiMe3)3·(THF)2]在戊烷中分解, 他们得到了元素分析结果上符合[Er(CH2SiMe3)(CHSiMe3)]组成的配合物(图1)[22]. 但以上3 个配合物都没有X 射线单晶表征的支持, 其具体结构也无从了解, 对这些配合物反应化学的研究也没有文献报道.图11.1稀土桥联碳卡宾配合物第一例结构明确的, 含[CH2]2−碳卡宾基团的稀土配合物直到2006 年才由Anwander 小组报道. 他们发现烷基稀土和烷基铝的加合物{Cp*Y[(μ-Me)2-AlMe2](μ-Cl)}2 和{Cp*6La6[(μ-Me)3AlMe]4(μ3-Cl)2 (μ2-Cl)6}在四氢呋喃作用下, 逐渐分解生成[Cp*3Ln3(μ-Cl)3(μ3-Cl)(μ3-CH2)(THF)3](Ln = Y 和La) (图2). 在这两个配合物中, 具有强反应性的[CH2]2−碳卡宾基团通过与3 个稀土离子Ln3+的桥联配位作用而被稳定. 在钇配合物中, 桥联碳卡宾基团的碳原子到金属钇离子的键长为2.424(2)~2.450(2) Å, 明显短于稀土桥联甲基配合物[(1,3-Me2(C5H3)2Y(μ- Me)]2 中桥联甲基与金属离子的键长(av. 2.61 Å), 而接近于离子型稀土甲基配合物[Y(CH3)(THF)6]2+ [BPh4]22−中末端甲基与金属离子的键长(2.418(3) Å). 该配合物可以发生与Tebbe 试剂[Cp2Ti{(μ对羰基的亚甲基转移反应, 还可以催化δ-戊内酯开环聚合反应.图21.2稀土Pincer 型碳卡宾配合物由于稀土金属-碳双键高度活泼, 含稀土金属-碳双键的稀土末端碳卡宾配合物很不稳定, 非常难合成, 而这类配合物又具有很重要的意义. 因此, 一些研究小组在它的模拟物上做了相当多的研究工作, 希望能帮助了解稀土金属-碳双键的性质和反应性能.2008~2010 年, Liddle 等利用该Pincer 型配体, 合成了多个稀土Pincer 型碳卡宾配合物 (图3). 在对稀土Pincer 型碳卡宾配合物 [Y(C(Ph2P= NSiMe3)2)(Bn)(THF)]与二苯甲酮反应的研究中, 他们发现反应中发生的是稀土金属与苄基间的金属-碳单键对二苯甲酮的羰基进行加成反应生成烷氧基配合物[Y(C(Ph2P=NSiMe3)2)(OCPh2Bn) (THF)], 而不是稀土金属- 碳双键参与了反应. [Y(C(Ph2P=NSiMe3)2)(Bn)(THF)]与偶氮苯反应的情况类似, 稀土金属-碳单键对偶氮苯的N=N 基团进行加成反应(图4). 这些反应说明这种Pincer 型碳卡宾配合物中稀土金属-碳双键的反应性还要低于稀土金属-碳单键的反应性能. 因此, 稀土Pincer 型碳卡宾配合物虽然相对易于合成, 但其反应性能显然要低于理想中的稀土末端碳卡宾配合物.图3图42.稀土氮卡宾配合物2.1稀土桥联氮卡宾配合物2009 年, 张洪杰和李兴伟等通过二价钐配合物和偶氮苯的氧化-还原反应, 得到了一个具有立方烷结构的稀土桥联氮卡宾配合物 (图5).1999 年, 谢作伟等在Me2Si(C9H7)(C2B10H11)与4当量NaNH2反应的THF溶液中, 加入1 当量的LnCl3,得到四核的氮卡宾簇合物[{(η5-μ2-C9H6SiMe2-NH)Ln}2(μ3-Cl)(THF)]2(μ4-NH)(THF)n (n = 1, Ln = Gd,Er; n = 0, Ln = Dy). 在这些配合物中, [NH]2−卡宾基团与4 个稀土金属离子配位.随后, 谢作伟等以(ArNH)2Yb(μ-NHAr)2Na(THF)(Ar = 2,6-iPr2C6H3)与 2 或 4 当量的n-BuLi 反应,得到稀土桥联氮卡宾配合物{(ArN)(ArNH)Yb(μ-NAr)}2{[Li(THF)][Na(THF)]}2 和{(ArN)2Yb(μ-NAr)}2{[Li2(THF)][Na(THF)]}2 (图6)[40]. [NAr]2−卡宾基团与两个稀土金属离子, 或与一个稀土金属离子和两个碱金属离子配位. 其中以后一种配位模式存在的,其Yb-N 键具有较显著的双键特征.图5图62.2稀土末端氮卡宾配合物近年来, 我们小组基于配体的立体效应和电子效应的考虑, 设计合成了一类新型的三齿氮配体, 这类配体可以很好地稳定高活性的稀土双烷基配合物. 进而我们利用这类配体合成了钪的烷基胺基配合物, 该烷基胺基配合物在外加Lewis 碱DMAP(DMAP = 4-二甲胺基吡啶)促进下, 发生烷基消除反应, 分离得到了第一例稀土金属末端氮卡宾配合物{Sc[MeC(2,6-(i Pr)2C6H3N)CHC(Me)(NCH2CH2NMe2)](2,6-(i Pr)2C6H3N)(DMAP)} (图7). X 射线单晶衍射结果显示, Sc-N(氮卡宾)双键的键长(1.881(5) Å)要比Sc-N(胺基)单键的键长(2.047(3) Å)短得多. 我们对相应的烷基胺基配合物和末端氮卡宾配合物分别进行了DFT 计算, 计算结果显示末端氮卡宾基团的两个p 轨道和钪离子的d 轨道重叠, 而胺基只有一个p 轨道和钪离子的d 轨道重叠.图7二、总结与展望稀土卡宾配合物化学是稀土金属有机化学的一个前沿领域, 近年来备受相关研究工作者的关注. 人们在这一方面进行了积极的探索, 合成得到了一些稀土桥联卡宾配合物和稀土卡宾配合物的模拟物.另外, 稀土钪末端氮卡宾配合物的合成, 表明了通过合理的设计, 稀土末端卡宾配合物是可以得到的. 接下来, 含大半径稀土金属离子的末端氮卡宾配合物的合成, 比稀土末端氮卡宾配合物更活泼稀土末端膦卡宾配合物, 以及稀土末端碳卡宾配合物的合成, 是摆在研究者前面的一个个挑战. 这些新型稀土金属配合物必然会具有不同于已知稀土金属配合的反应和催化性能. 对稀土卡宾配合物的合成, 反应和催化性能的研究, 不仅是对现有稀土金属有机化学的一个重要发展, 也是对整个过渡金属-主族元素多重键化学的一个重要补充和发展.参考文献1 钱长涛, 杜灿屏. 稀土金属有机化学. 北京: 化学工业出版社, 20042 Schumann H, Meese-Marktscheffel JA, Esser L. Synthesis, structure, and reactivity of organometallicπ-complexes of the rare earths in theoxidation state Ln3+ with aromatic ligands. Chem Rev, 1995, 95: 865–9863 Edelmann FT, Freckmann DMM, Schumann H. Synthesis and structural chemistry of non-cyclopentadienyl organolanthanide complexes.Chem Rev, 2002, 102: 1851–18964 Arndt S, Okuda J. Mono(cyclopentadienyl) complexes of the rare-earth metals. Chem Rev, 2002, 102:1953–19765 Rabe GW, Riede J, Schier A. Synthesis, X-ray crystal structure determination, and NMR spectroscopic investigation of two homolepticfour-coordinate lanthanide complexes: trivalent (t Bu2P)2La[(μ-P t Bu2)2Li(thf)] and divalent Yb[(μ-P t Bu2)2Li(thf)]2. Inorg Chem, 1996, 35:40–456 Hong S, Marks TJ. Organolanthanide-catalyzed hydroamination. Acc Chem Res, 2004, 37: 673–6867 Molander GA, Romero JAC. Lanthanocene catalysts in selective organic synthesis. Chem Rev, 2002, 102: 2161–21868 Shen Z, Ouyang J, Wang F, Hu Z, Yu F, Qian B. The characteristics of lanthanide coordination catalysts and the cis-polydienes preparedtherewith. J Polym Sci, Polym Chem Ed, 1980, 18: 3345–33579 Yasuda H. Organo-rare-earth-metal initiated living polymerizations of polar and nonpolar monomers. J Organomet Chem, 2002, 647:128–13810 Hou Z, Luo Y, Li X. Cationic rare earth metal alkyls as novel catalysts for olefin polymerization and copolymerization. J Organomet Chem,2006, 691: 3114–312111 Amin SB, Marks TJ. Versatile pathways for in situ polyolefin functionalization with heteroatoms: Catalytic chain transfer. Angew Chem IntEd, 2008, 47: 2006–2025。

科技英语写作语法错误举例

科技英语写作语法错误举例from: The ACS Style Guide: A Manual for Authors and Editors, Chapter 2, 1986 The ACS Style Guide: A Manual for Authors and Editors, 2nd Edition, 19971Subject-Verb Agreements例1 Application of this technique to studies on phytoplankton biomass and its environments are described.[说明] The subject is ―application‖, which is singular.Application of this technique to … is described.Sometimes, two singular subjects join ed by ―and‖ cause this error.例2 Growth and isolation of M13 virus was described.→Growth and isolation of M13 virus were described.Exception: A subject that is plural in form but singular in effect takes a singular verb.例3 The name and address of each contributor is given on the title page.例4 Research and development is attracting a growing number of young scientists.However, when two or more subjects are joined by ―or‖, the verb takes the number of the closest subject.例5 Application or uses were noted.Uses or application was noted.例6 The appropriate metal ion concentration or the rate constants were used.The rate constants or appropriate metal ion concentration was used.Collective nouns take a singular verb when the group as a whole is meant; in that case they are often preceded by the word ―the‖. Collective nouns take a plural verb when individuals of the group are meant; in that case, they are often preceded by the word ―a‖.contents majority rangecouple number seriesdozen pair varietygroup例7 The series is arranged in order of decreasing size.[说明] Refers to the series as a unit.例8 A series of compounds were tested.[说明] Refers to each compound.例9 The number of metal amides synthesized was the largest to date. (Refers to the number as a unit.)A number of metal amides were synthesized. (Refers to each amide.)例10 The series of compounds was prepared to test the hypothesis. (Refers to the series as a unit.)A series of compounds were tested. (Refers to each compound.)例11 A series of low molecular weight phenolphthalein epoxy resins ( M n＝500～700) hasbeen prepared from phenolphthalein and epichlorohydrin using K2CO3(Na2CO3)/H2O as catalysts instead of NaOH/H2O.→A series of low molecular weight phenolphthalein epoxy resin s (M n＝500～700) heve been prepared from phenolphthalein and epichlorohydrin using K2CO3(Na2CO3)/H2O as catalysts instead of NaOH/H2O.―Data‖ can be a singular or plural noun.例12 Experimental data that we obtained are compared with previously reported results.[说明] Refers to the data as individual results.例13 After the data are distributed, we can meet to discuss them.→After the data is distributed, we can meet to discuss it.[说明] Refers to the whole collection of data as one unit.例14 None of the samples were soluble.→None of the samples was soluble.[说明] Refers to individuals.例15 This group of workers are well aware of their responsibilities.→This group of workers is well aware of its responsibilities.[说明] Refers to the group as a unit.Units of measurement are treated as collective nouns and therefore take a singular subject.例16 The mixture was stirred, and 5 mL of diluent were added.→The mixture was stirred, and 5 mL of diluent was added.例17 Five grams of NaCL were added to the solution.→Five grams of NaCL was added to the solution.例18 Three weeks are needed to complete the experiment.→Three weeks is needed to complete the experiment.Nouns ending in ics and denoting a scientific discipline are usually singular.dynamics mechanicskinetics physicsmathematics thermodynamicsMechanics involves the application of Newton’s three laws of motion.The kinetics of electron transfer to and from photogenerated radicals was examined by laser flash photolysis.The thermodynamics is governed by the positions of the valence and conduction bands.Compound subjects containing the words ―each‖, ―every‖, and ―everybody‖ may take singular verbs.例19 Each flask and each holder was sterilized before use.Both components of the compound subject must contain the words in question. Otherwise, the verb must be plural.例20 Each student and all of the professors were invited.Sometimes, one of these words is implicit; such cases take a singular verb.例21 Each name and address is entered into the database.Indefinite pronouns themselves (or adjectives combined with the indefinite pronoun ―one‖) can be the subject of the sentence.• Those that take a singular verb are ―each‖, ―either‖, ―neither‖, ―no one‖, ―every one‖, ―anyone‖, ―someone‖, ―everyone‖, anybody‖, somebody‖, and everybody‖.例22 Each was evaluated for its effect on metabolism.例23 Neither disrupts the cell membrane.例24 Regarding compounds 1—10, every one reacts with the control agent.例25 Someone measures the volume every day.• Those that take a plural verb are ―several‖, ―few‖, ―both‖, ―’and ―many‖.例26Several were evaluated for their effects on metabolism.例27Few disrupt the cell membrane.例28Regarding compounds 1 and 2, both react with the control agent.例29Many were chosen to be part of the study.• Those that take either a singular or plural verb, depending on context, are ―some‖, ―any‖, ―none‖, ―all‖, and ―most‖. The number of the object of the preposition determines the number of the indefinite pronoun related to it.例30Some of the money was stolen.例31Some of the books were lost.例32Not all the disks are here; some were lost.When a fraction is the subject of the sentence, the number of the attendant object of the preposition determines the number of the subject.例33One‐third of the precipitate was dissolved.例34One‐fourth of the electrons are excited.例35The remainder of the compounds are yet to be described.When a subject and its predicative disagree in number, the verb takes the number of the subject.例36The preparation and structure determination of these three compounds are the topic of paper.例37The topic of this paper is the preparation and structure determination of these three compounds.2 Restrictive and Nonrestrictive ClausesWhen a clause in a compound sentence is restrictive, the clause is necessary to the sense of the sentence, the sentence would become pointless without the clause. Restrictive clauses are best introduced by ―that‖, not ―which‖.例38 It was necessary to fined a blocking group which would react with the amino groupbut not with the hydroxyl.→It was necessary to fined a blocking group that would react with the amino group but not with the hydroxyl.A phrase or clause is nonrestrictive if it adds information but is not essential ; that is, thesentence does not lose its meaning if the phrase or clause is deleted.Nonrestrictive phrase and clause are set off by commas.例39The current-voltage curves, which are shown in Figure 6, clearly demonstrate the reversibility of all four processes.例40Melvin Calvin, who won the Nobel Prize in 1961, elucidated the biochemical pathways in photosynthesis.3Dangling Modifiers （悬垂修饰语）何谓Dangling Modifiers （悬垂修饰语）• A dangling modifier is a word or phrase that does not clearly and logically modify another word in the sentence. In scientific writing, passive voice is often necessary (―the solutions were heated‖; melting points were determined‖), but its use can lead to dangling modifiers.• The understood subject is usually the same as in the main clause.Walking across the field, we saw a plane fly past.(= As we were walking …,we saw …)• 与句子主语没有联系的短语修饰语，即动词短语的逻辑主语（隐含主语）与主句主语不一致。

一种新型的手性螺环化合物的合成及其结构的确定

一种新型的手性螺环化合物的合成及其结构的确定山西大学(自然科学版)23(1):50～53,2000JournalofShanxiUnlⅢsnv(Nat.SciEd)文章编号:0253—2395(2000)010050040一一种新型的手性螺环化合物的合成及其结构的确定陈良威齐丽琴/张永梅邓并(山西太学化学系,山西太原030006)摘要:手性化舍物的告成厦其螺旋结构与光学活性的关系的研究,是当夸有机化学发展中的前沿课题之一本项工作般R(+)1,1'一联一2一幕酚为原料,在有机碱的催化下与T2-1~L氯环合,得到联二萘酚螺环酯粪衍生耪.井结合已有的研完工作,根据x衍射结构,利用NMR,IR,MS,0V等剥试手段,确定出了产物的结构.邵,2萘酚1与二卤代烷X一(CH)一X(x—CI,Br或I;n=1～6)环合:,得到联二萘酚环醚系列衍生物2-I相应地,还此R一(+)一l,1'一联一2一萘酚1与二酰氯试剂CICO(CH.)COCI(n=0,3,4,6)反应得到大环酯化合物3(式1).同时,培养出了这两个系列化合物的单晶,并测试出了它们的x一衍射结构..no式1我们也试图用丁二酰氯与此R(+)1.1一联一2一萘酚1反应,以期规律性地得到化台物4,然而却意外地得到螺环化台物5和6(式2).这与本研究组在前期用1与邻苯二甲酰氯反应得到的化合物7具有类似的结构(式3)'.显然,1,l一联一2一萘酚与含有骨架COC—C—CO一的二酰氯的反应是一类特殊的反应.因此,不断摸索和改进实验条件,利用这种特殊的有机反应方式,来合成并分离得到化台物5和6,具有一定的理论意义和实用价值.收辅日期:1999一∞一11基金项目:国家教委忧秀青年教师基金;山西省归国留学人员基金资助课题.作者筒介:陈良威(1976)t男一1999年7月毕业于山西太学化学系:*邛井(1959一),女.1991年12月毕业于德国汉诺威太学化学系,获博士学位.1992年2月至1994年12月在北京大学化学系做博士后研究.现为山西太学化学系尉教授,硕士生导师,主要从事有机台成厦立体化学的科研和教学工作.～胨良威等:一种新型的手性螺环化台物的台成及其结构的确定式2式381结果与讨论本研究在前人工作的基础上,采用极度稀释技术,对实验条件和产率进行了.摸索和尝试.为降低实验费用,在实验条件的摸索过程中,均采用外消旋的联二萘酚代替光学纯的联二萘酚.11滴加方式的选择首先在室温下,以三乙胺作催化剂,就滴加方式进行选择.最佳方式为:将丁二酰氯的无水乙醚溶液缓慢地向装有等摩尔的1,1联一2一萘酚1与一定量三乙胺乙醚溶液的混合液中滴加,中途检测,TLC显示三个点(含原料点),原料点上,下各有一个点.滴毕,经后处理,用柱色谱分离,得原料上点和原料下点,经NMR,MS,IR等谱推测为化合物6和5.1.2柱色谱分离条件的选择为了将反应产物彻底分离,实验中对柱色谱分离条件进行了探索,最后选取规格为30cm×3cm的色谱柱,以硅胶作吸附剂用石油醚:乙醚一7:1装柱,洗脱剂比例开始为石油醚:乙醚=4;1,逐渐增至1.5:1.1.3产物结构的确定结合x一衍射数据和"C—NMR谱,我们发现:凡是结构为醚系列2和酯系列3的太环化合物,其碳原子总数N为偶数时,"C—NMR图谱显示其峰数P=N/2}当N为奇数时,P一(N+1)/Z(见表1).这表明,由于一对称性的存在,分子内的一半碳原子与另一半具有相同的化学位移值.寰1醚系列2和蠢系列3各化台物碟原子总数N爰其对应C—NMR谱■救P 醛系列2醇系列3N2122232'4252622252628Pl111121213l31113l314但是,化合物8以及在以往工作中得到的化合物9,均为螺环化合物(附X一衍射结构图,图.1),其C—NMR图谱显示相应的峰效均与总碳数相等.本实验主要产物5的"C—NMR图谱有24个特征峰,说明分子内已无C2-对称性,假想其结构为螺环酯类化合物5.推测结果与其波谱数据及高分辨图谱完全吻合(见实验部分).期鹳嚣山西大学(自然科学版)孕oH3CCI囤1化舍物B和9及其x一桁射结构图总之,我们合成了化合物5和6,并确定了它们的结构.我们认为这是一种新型的生成手性螺环化合物的方法,也就是说,当分子中出现如式4所示的结构时,反应将向生成螺环产物的方向进行.反应机理正在研靠和探讨之中.2实验部分2.1仪器与试剂式4SanyoGallenkampMPD350.BM2.5熔点测定仪;PerkinElmer241旋光仪;VazioEL元素分析仪}PE一1800红外光谱仪;BrukeARX.400核磁共振仪;VG—ZAB—HS质谱仪}ZabspecTofspecPlatform—ESI质谱仪;薄层色谱板(Silica60F254withFluorescentIndicator).R一(+)一l,1一联一2一萘酚,[d]D一一34.3(cl,THF)m.P.208.0～209.9"C;丁二酸,五氯化磷,三乙胺(AR);柱层析硅胶(青岛,160—200目);溶剂均经无水处理2.2丁二酰氯的镧备口向250mL烧瓶中依次加入30mL氯仿,30g(0.25too1)丁二酸,105gPC1(O.5too1),搅拌.反应剧烈放热并加热回流成液态后,蒸去低沸物,回收氯仿.减压蒸馏,除尽磷的化合物,收集95～1IO~C/20mmHg(2666.4P)馏分,得23.25g(0.15too1)产品(见式5).收率60.CH2COOHrHri,CH2COI2ll+Pcl5_二=lCHO0HCHCOC12.3R一(+)一1,1'-联一2一萘酚1与丁二酰氯的环合作用于1000mL三颈圆底烧瓶中加入无水乙醚350mL,三乙胺 6.5mL和2.86g(0.01mo1)1,1一联2二萘酚,室温下搅拌到固体全部溶化.然后,向此溶液中缓慢滴加350mL无水乙醚稀释的1.1mL(0.01too1)丁二酰氯溶液,历时24h.反应混合物经抽滤除去沉淀后,加入2tool?L一柠檬酸水溶液洗涤,分出有机相,再依次以饱和NaHCO和NaCI水溶液洗涤,无水NaSO一NaCO.干燥.过滤,旋转蒸发除去溶剂,得粗产品0-8g,用乙醚和二氯甲烷溶解,柱色谱分离(洗脱剂:石油醚/乙醚=4:1至1.5:1),得化合物50.122g,产率为3.3和化合物60.048g,产率为1.2.化合物5m.P.291.0℃,Rft.,vt一】=0.56.1_a]D=+76.0(c1.27,CHC12).IR(KBr):3424(b,w),胨良威等:一种新型的手性螺环化台物的台成及其结构的确定3063(w),1868(vs),1435(m),1226(vs),1130(s),809(m)cm一.UV(CH2C1￡):227.2nm,290.8nm.H—NMR(400MHz,CDCoCD):2.83—2.8O(2H,m),2.88—294(2H,m),8.00(2H,d,J一8.6Hz),8.32(2H,ddd,J一8.9Hz,J一8.0Hz,J—1.3Hz),8.53(2H,ddd.J一9.9Hz,J一8.2Hz,J一1.1Hz),8.80(2H,d,J一9.OHz),8.O9(2H,d,J=8.2Hz),8.21(2H,d,J一8.9Hz)."C—NMR(1OOMHz,CDCOCD):l8.52,27.5O,33.44,34.59,35.95,36.8l,126.38,126.73,126.99,130.66,13O.93,131.34,131.49,131.54,1 31.61,l32.13,133.48,133.75,135.36,l35.65,136.81,l38.57,153.16,174.40.MS(EI):m/z368(M,l 9),268(100),239(15),101(21),43(48).高分辨质谱:cH.6O4,计算值:368.10465.实测值:368.10486化合物6m.P.141.0℃～142.0℃,RfE肫L一0.56.IR(KBr):3116(b,w),3053(w),1800(vs),1622(m),12g4(vs),965(vs),819(s)cm一.UV(CH2Ck):227.2nm,309.6rim.H—NMR(400MHz,CDC0(2D):8.4l一8.48(2H,m),8.52(2H,t,J一8.1Hz),8.58—8.62(2H,m),8.62(2H,t,J一8.8Hz),8.86(1H,s),8.13(2H,d,J一8.4Hz),8.21(2H,d,J一8.8Hz)."C—NMR(100MHz,CDCOCD):114.76,1l9.14,123.22,123.76,l25.32,125.38,126.44,126.76,127.07,l27.35,128.85,l29.04,129.07,129.55,129.9 3,130.78.132.92,134.64,l34.79,148.43,153.65,170.64.MS(EI):m/z400(M,85),268(100),239(63), 134(23).高分辩质谱:cHzso;.cl,计算值:400.05024.实测值:400.04973.致谢在车课题的研究过程中,得翻了丁景范,张昭郭炜等老师的悉心指导和热情帮助,在此表示感谢参考文献HUANGJJ,ZHANGH,DENGB.SynthesisofCyclicEtherDerivativesofR一(+)一1,ir_blnaphthyl一2,2r_diolandTheirHeti~tStrttctuteaadOpticalRotatloa[A].The8thlnter~atioBalSymposRtmonFineChemis tryandFuneitiona[Polv—mers[C].ShanxiScienceandTechnologyPress,Taiyuan,1998.46.张红,黄计军,高照渡,齐丽琴,张建明,邓并.S-(一)…221联二萘酚衍生物的台成及其螺旋结构与旋光性的关系D].化学.1999.57(6):635.HUANGJJ,XUEF,DENGB,ThomasCWMak,HelicalSturctureandOpticalActivityofTwoNewDerivativesofR一(+)一1,1一Binaphthyl一2,2-dialD].ChineseChemLt,1998,9(I2):1081.wuYD,yANYL(Ed).HelicalStructureandOpticalRotationofEsterDerivaticvesofR(+1)一1.1一binaphthy1—2.2一diol[A].SymposiumonFrontiersofChemistryinConjunctionwithTheSecondConference ForWorldwideChineseY oungChemistsEC].TheHongKongUniversityofScienceandTechnology,HongKong.19 97.241.樊姥廷编着.有机合成事典[M].北京:北京理工大学出版杜出版,1992.38. SynthesisofaNewTypeChiralSpiranes andtheDeterminationofTheirStructures CHENLiang—weiQILi—qinZHANGY ong—meiDENGBing (DepartmentofChemistry,ShanxiUniversity,Taiyuan030006,China)Abstract:Nowadaysthesynthesisofchiralcompoundsandtheinvestigationoftheirrelations hiDhetween helicalstructureandopticalactivityarethehighlightsinthefieldoforganicchemistrY. Inthisresear℃htheR一(+)一1,1'-bi一2一naphtholwascyclizedwithsuccinylchlocideinthepresenceofNEtinabsoluteetherarld anewkindofspiranederivativesofnaphtholwereobtained.Basedonourpreviousw0rksandt hedata0fX—raydiffractionthestructuresoftheproductsweredeterminedwiththehelpofmodernphysica 1meth0dsofNMR,IR,MSandUVect..Keywords:R一(+)-1,1一bi一2一naphthol;succinylchlocide;sDirane叫啪嘲Ⅲ嗍。

基于数据的综合评价方法研究

摘要摘要综合评价是对多属性体系结构描述的对象系统做出全局性、整体性的评价，它是资源管理、复杂系统优化等众多实际问题的核心内容。

由于计算机的发展和相关领域的不断深入研究，综合评价方法在社会、经济、科技、教育、环境和管理等领域得到了广泛应用。

在综合评价问题中，属性权重的确定以及评价模型的构建是最重要也是最困难的问题。

信息系统是一个具有对象和属性关系的数据库，数据库中的数据是社会经济发展中的各个领域必须依据的信息，但这些数据信息存在着各种各样的不完备性。

由于数据中隐含着对象和属性之间的关系，这种关系需要依赖一定的数学方法和计算工具才能挖掘出来。

而Pawlak 在1982年提出的粗糙集就可以很好地解决此类问题，它可以帮助人们利用积累的数据信息，在信息系统中不断发现新的知识，并使这些知识辅助于评价和决策过程。

本文针对综合评价问题中属性的重要性难以确定的问题，以决策信息系统为依托，以隐藏在数据中的知识为支撑，以属性集的变化所导致的知识的变化为依据，构建了一种满足模糊测度结构特征，反映属性关联性和重要性的度量机制。

进而以此为基础，以Choquet模糊积分作为信息融合的工具，建立了一种基于决策信息系统的综合评价模型，并且结合具体案例分析了该方法的特点。

结果表明，该方法不仅与现有的综合评价方法具有本质的区别，而且具有良好的可操作性和可解释性，在资源分配、绩效评价、复杂系统优化等领域具有广泛的应用价值。

关键词综合评价；决策信息系统；模糊测度；评价模型；属性重要性I河北科技大学硕士学位论文AbstractComprehensive evaluation is to assess objects with the description of multi-attributes structure from a global perspective. It plays an important role in resource management, complex system optimization and other practical problems. Since the development of computer and the intensive study in related fields, the methods of comprehensive evaluation have found many applications in society, economic, technology, education, environment and management. How to determine attribute weights and construct evaluation model are two critical problems in the process of comprehensive evaluation.Information system is a database with objects and attribute relations. All fields in social and economic development are highly dependent on data, but the data information is always incomplete. Data in database contain relations between objects and attributes. This kind of relations can be discovered by certain mathematical methods and computing equipments. The rough set theory proposed by Pawlak in 1982 is helpful to solve this kind of problems. By using it, the accumulated data information can be utilized to discover new knowledge from information systems, thus assisting evaluation and decision making.In order to determine the significance of attributes in comprehensive evaluation, we study the metric of attributes correlation based on changes of knowledge induced by that of attributes sets in decision information systems, and construct the determination mechanism of attributes interactions, which not only reflects the significance measures, but also satisfies the structure characteristics of fuzzy measure. Further, by taking Choquet integral as synthesis operator, we construct the comprehensive evaluation model based on decision information system. Finally, we analyze the features and effectiveness of the proposed model with case study. The results show that the method is different essentially comparing with the existing ones and also has good operability and interpretability. Moreover, it can be applied in the fields such as resource allocation, performance assessment and complex system optimization.Key words Comprehensive evaluation; Decision information system; Fuzzy measure;Evaluation model; Attribute significanceII目录目录摘要 (I)Abstract .................................................................................................I I 第1章绪论. (1)1.1 研究背景与意义 (1)1.2 国内外研究现状及发展趋势 (1)1.2.1 粗糙集理论的发展概述 (1)1.2.2 特征选择的研究现状 (5)1.2.3 综合评价方法的研究现状 (7)1.3 问题的提出 (10)1.4 论文的研究内容 (11)1.5 论文组织结构 (11)第2章粗糙集的相关理论 (13)2.1 粗糙集的基本概念 (13)2.2 本章小结 (17)第3章基于大型数据集的特征选择方法 (19)3.1 信息系统中的划分差异熵 (19)3.2 基于划分差异熵的特征选择 (23)3.3 实验分析 (27)3.4 本章小结 (30)第4章基于离散型数据的综合评价方法 (31)4.1 基于核心示例集的属性重要性度量 (32)4.2 基于离散型数据的模糊综合评价模型 (34)4.3 案例分析 (36)4.4 本章小结 (40)第5章基于连续型数据的综合评价方法 (41)5.1 基于邻域覆盖信息系统的隐含重要性度量 (41)5.2 属性的综合重要性度量 (43)5.3 基于连续型数据的综合评价模型 (44)5.4 案例分析 (45)5.5 本章小结 (50)结论 (51)III河北科技大学硕士学位论文参考文献 (53)攻读硕士学位期间发表的论文 (57)致谢 (59)IV第1章绪论1.1研究背景与意义综合评价方法或多属性决策是项目管理、人才选拔、绩效评估等领域广泛面对的问题，如何构建具备科学性和可操作性的评价方法一直是学术和应用领域的热点研究内容。

罗伯特·伍德沃德：有机合成化学的泰斗

罗伯特·伍德沃德：有机合成化学的泰斗Robert Woodward: A Titan in Organic SyntheticChemistryRobert Woodward, a titanic figure in the realm of organic synthetic chemistry, has left an indelible mark on the scientific community. His contributions to this field are nothing short of legendary, pushing the boundaries of knowledge and opening new horizons for future generations.Woodward's journey into science began with a deep fascination for chemical reactions and their intricate patterns. He was fascinated by how different compounds could be transformed into entirely new substances through careful manipulation. This passion led him to delve deeper into the mysteries of organic synthesis, a complex yet rewarding domain that requires meticulous planning and execution.One of his most significant achievements lies in his groundbreaking work on the synthesis of natural products. These complex molecules, often found in plants or animals, have been the holy grail of synthetic chemists for decades. Woodward, however, wasn't daunted by the challenge. Through his ingenious approach and unwavering determination, he successfully crafted numerous natural product analogs, offering valuable insights into their structure-activity relationships.His influence extends beyond the laboratory walls. As a mentor and advisor, Woodward inspired countless young scientists to pursue their passions in chemistry. His advice was always practical and insightful, guiding students towards success while encouraging them to maintain their curiosity and creativity.In recognition of his outstanding contributions, Woodward received numerous accolades and honors from various institutions around the world. However, he remained humble and dedicated to his craft, always seeking new challenges and opportunities to expand the frontiers of knowledge.Today, as we celebrate Robert Woodward's legacy, it is important to remember not only his scientific achievements but also his impact on the lives of those who knew him. His dedication to science, passion for discovery, and selfless mentorship will forever serve as inspiration for future generations of chemists.。

含苯并咪唑基配体钴(Ⅱ)配合物的合成、晶体结构和儿茶酚酶活性

含苯并咪唑基配体钴(Ⅱ)配合物的合成、晶体结构和儿茶酚酶活性张前;韩燕;焦元红【摘要】合成和表征了一种钴(Ⅱ)配合物,[CoLCl]2[CoLCl0.5(H2O)0.5]2ClO4·10H2O(1)(LH=(2-(二((1H-苯并咪唑-2-基)甲基)氨基)乙酸)).以3,5-二叔丁基儿茶酚(3,5-DTBC)为反应底物,用紫外光谱测试了1的儿茶酚酶催化活性.研究结果表明:在配合物的晶体结构中,不对称单元的2个Co(Ⅱ)都形成变形的三角双锥构型.在pH=5～11范围内,配合物1对3,5-DTBC 的氧化显示了pH值依赖性,它的儿茶酚酶催化活性随着温度的升高而升高,并且其催化氧化3,5-DTBC的动力学符合米氏方程模型.【期刊名称】《无机化学学报》【年(卷),期】2016(032)001【总页数】8页(P131-138)【关键词】钴(Ⅱ)配合物;晶体结构;儿茶酚酶;催化活性【作者】张前;韩燕;焦元红【作者单位】湖北理工学院化学与化工学院,黄石 435003;新乡学院化学化工学院,新乡 453003;湖北理工学院化学与化工学院,黄石 435003【正文语种】中文【中图分类】O614.81+2Catecholase(EC 1.10.3.1)is a type-3 copper enzyme usually encountered in plant tissues and in some insects and crustaceans.It catalyzes the oxidation of a broad range of o-diphenols to the corresponding o-quinones coupled with the reduction of oxygen to water[1].Catecholase is of economic importance due to its help to protect damaged plants against both bacterial and fungal disease.In the crystal structure of catecholase isolated from Ipomoea batatas(sweet potato),the active site contains a binuclear copper(Ⅱ)center,and each copper(Ⅱ)ion is coordinate d by three imidazole nitrogen atoms from three histidine units[2]. It′s inspired numerous scientists to study the structure-activity relationships of catecholase. Benzimidazole could mimic the histidine residue owing to its same imidazole group,and recently many catecholase model complexes containing benzimidazole and imidazole ligands have been reported based on their active sites[3-8].The synthesis of artificial catecholase could provide a deeper insight into the structure, catalytic activity and mechanism of the natural catecholase,and it helps us to design more effective catecholase models.Herein,we report the synthesis and crystal structure of a cobalt(Ⅱ)complex(1) containing benzimidazoleligand.Furthermore,its catecholase catalytic activity was investigated using 3,5-di-tert-butylcatechol(3,5-DTBC)as the substrate.1.1 Materials and physical measurementsAll reagents were purchased from commercial companies and directly used unless stated otherwise. The melting point was determined with an XT4A micromelting point apparatus and was uncorrected. The pH value wasadjusted by PHS-3C digital pH meter.UV-Vis spectra were measured on an Analytik jena Specord 210 spectrophotometer.The IR spectra were carried out on a Perkin-Elmer Spectrum BX FTIR instrument in tablets with potassium bromide. Elemental analyses were examined on a Perkin-Elmer 2400 instrument.Electrospray ionization mass spectra (ESI-MS)were performed on an Applied Biosystems API 2000 LC/MS/MS system.1H NMR spectra were recorded on a Varian Mercury 400 spectrometer at 400 MHz.1.2 Synthesis of the ligand LHThe two-step synthesis of the ligand LH is outlined in Scheme 1.The intermediate bis(benzimidazol-2-ylmethyl)amine(a)were prepared according to the literature method[9].The ligand LH was synthesized usinga modified literature procedure[10].25 mL of sodium hydroxide aqueous solution (0.02 mol·L-1)was added dropwise to a mixture of chloroacetic acid(0.95 g,10 mmol)and the intermediate a(2.77 g,10 mmol)in ethanol(100 mL).The resulting mixture was stirred rapidly and refluxed for 6 hours,then the solvent was evaporated to give the crude product,which was dissolved in water and filtered.The solution was acidified to pH 3～4 with hydrochloric acid(0.1 mol·L-1)and further filtered to obtain the white product.Yield:2.18g(65%).1H NMR(DMSO-d6,400 MHz):3.42(s,2H),4.28(s,4H),5.06(s,2H),7.25～7.61(m,8H),10.78(s,1H). ESI-MSm/z:335.20(M+).Anal.Calcd.forC18H17N5O2(%):C,64.47;H,5.11;N,21.88.Found(%):C, 64.28;H,5.41;N,21.42.1.3 Synthesis of the cobalt(Ⅱ)complex(1)The ligand LH(0.34 g,1 mmol)was dissolved in methanol(40 mL),and the resulting solution was adjusted pH value to 8.0 using 0.5 mol·L-1NaOH. Then CoCl2·6H2O(0.24 g,1 mmol)and NaClO4(0.12 g,1 mmol)were added to the stirred solution at 333 K for 6 hours.The solution was cooled to room temperature and filtrated to remove the insoluble substance.Red crystals suitable for X-ray diffraction studies were obtained after five days.m.p.214～216℃.UV-Vis spectra(MeOH solution):278 nm(ε= 24 400 L·mol-1·cm-1).IR(KBr,cm-1):3 025(m),2 942(s),1 716(s),1 545(s),1 460(s),1 405(s),1 056 (m),755(m).Anal.Calcd.for C72H86N20O23Co4Cl4(%):C,43.70;H,4.35;N,14.16.Found(%):C,43.34;H, 4.08;N,14.42.1.4 Synthesis of the other complexes(2～7)The other preparations of transition metal(M n(Ⅱ),2;Fe(Ⅱ),3;Ni(Ⅱ),4;Cu(Ⅱ),5;Zn(Ⅱ),6)complexes containing the ligand LH were similar to the cobalt(Ⅱ)complex(1)using metalchlorides(namely,MnCl2· 4H2O,FeCl3·6H2O,NiCl2·6H2O,CuCl2·2H2O,ZnCl2), but NaClO4was not added.The dicobalt(Ⅱ)complex[Co2(EGTB)(NO3)2(DMF)2](NO3)2·2DMF(7)was prepared according to the literature[11].[MnLCl](2):Grey crystalline powder.Yield:53%, m.p.282～284℃.UV-Vis spectra(MeOH solution): 282 nm(ε=22 840 L·mol-1·cm-1).Molar conductance, ΛM:(DMF,S·cm2·mol-1)12.5.IR(KBr,cm-1):3 044 (m),2 935(s),1 722(s),1 578(s),1 452(s),1 412(s), 1 066(m).ESI-MSm/z:424.54(M+).Anal.Calcd.forC18H16N5O2MnCl(%):C,50.88;H,3.77;N,16.49.Found(%):C,51.14;H,3.52;N,16.02.[FeLCl]Cl(3):Orange crystalline powder.Yield: 42%,m.p.＞300℃.UV-Vis spectra(MeOH solution): 276 nm(ε=24 510 L·mol-1·cm-1).Molar conductance, ΛM:(DMF,S·cm2·mol-1)72.8.IR(KBr,cm-1):3 012 (m),2 936(s),1 755(s),1 568(s),1 444(s),1 408(s), 1 036(m).ESI-MSm/z:425.56(M+).Anal.Calcd.forC18H16N5O2FeCl2(%):C,46.85;H,3.47;N,15.18.Found(%):C,47.08;H,3.89;N,14.86.[NiLCl]·2H2O(4):Pale-green crystalline powder. Yield:62%,m.p.252～253℃.UV-Vis spectra(MeOH solution):272 nm(ε=20 980 L·mol-1·cm-1).Molar conductance,ΛM:(DMF,S·cm2·mol-1)9.6.IR(KBr, cm-1):3 048(m),2 955(s),1 762(s),1 526(s),1 438(s), 1 402(s),1 048(m).ESI-MS m/z:428.51(M-2H2O)+. Anal.Calcd.for C18H20N5O4NiCl(%):C,46.53;H,4.31;N,15.08.Found(%):C,46.16;H,4.22;N,15.56.[CuLCl](5):Green crystalline powder.Yield:58%, m.p.＞300℃.UV-Vis spectra(MeOH solution):276 nm(ε=24 380 L·mol-1·cm-1).Molar conductan ce,ΛM: (DMF,S·cm2·mol-1)11.2.IR(KBr,cm-1):3 052(m), 2 938(s),1 762(s),1 555(s),1 428(s),1 412(s),1 026 (m).ESI-MSm/z:433.14(M+).Anal.Calcd.forC18H16N5O2CuCl(%):C,49.88;H,3.67;N,16.17.Found(%):C,50.14;H,4.02;N,16.62.[ZnLCl](6):Pale-yellow crystalline powder.Yield: 54%,m.p.＞300℃.UV-Vis spectra(MeOH solution): 278 nm(ε=20 850 L·mol-1·cm-1).Molar conductance, ΛM:(DMF,S·cm2·mol-1)11.8.IR(KBr,cm-1):3 048 (m),2 944(s),1732(s),1 568(s),1 466(s),1 422(s), 1 014(m).ESI-MSm/z:434.55(M+).Anal.Calcd.forC18H16N5O2ZnCl(%):C,49.71;H,3.68;N,16.11.Found(%):C,49.48;H,3.26;N,16.58.1.5 Structure determ ination of com p lex 1Red crystal of compound 1 having approximate dimensions of 0.30mm×0.30 mm×0.20 mm was mounted on a glass fiber in a random orientation at 298(2)K.The determination of unit cell and the data collection were performed with Mo Kα radiation(λ= 0.071 073 nm)on a Brucker Smart-2000 CCD diffactometer.A total of 16 976 reflections were collected in the range of 1.63°<θ<25.68°at room temperature. The origina l data were integrated and corrected for Lorentz polarization effects using SAINT program and were corrected for absorption effects[12-13].Structures were solved by direct methods using SHELXS-97,and all non-hydrogen atoms were directly located from difference Fourier maps and successfully refined with anisotropic displacement parameters[14].The coordinates of hydrogen atoms only participated in the structure factor calculation and not included in the refinement. Hydrogen atoms in the complexes were placed in idealized positions,and those in water molecules were located in the difference Fourier maps.The Cl(2)and O(5)are both half occupancy.Due to the Cl(2)is too close to O(5),it was necessary to apply SIMU restraints to the O(5)to avoid the high ellipsoid in O(5). Because the guest solvent molecules are highly disordered and impossible to refine using conventional discrete-atom models,the QUEEZE subroutine of thePLATON software suite was applied to remove the scattering from the free water molecules[15].A SQUEEZE analysis showed that the void space was occupied by 104 electrons per formula,corresponding to 10 water molecules per formula unit.The number of free water molecules were also determined by element analysis. The final R=0.045 9 and wR=0.150 2(I＞2σ(I)),S= 1.122,(Δ/σ)max=0.001,(Δρ)max=852 e·nm-3and(Δρ)min=-375 e·nm-3.Crystal data and structural refinement were listed in Table 1.The selected bond lengths and bond angles were summarized in Table 2,and the hydrogen bond lengths and bond angles were given in Table 3. CCDC:950329,1.1.6 Catecholase m im ic activity3,5-di-tert-butylcatechol(3,5-DTBC)was used as the substrate to investigate the catalytic activity of the catecholase model complex[7].Kinetic experiments for the oxidation of 3,5-DTBC were performed spectrophotometrically on a Analytik jena Specord 210 spectrophotometer by the characteristic absorption band of the expected product,3,5-di-tert-butyl-obenzoquinone,at 400 nm.Freshly prepared stock solutions of the complex(0.10 mmol·L-1)and 3,5-DTBC(1.0 mmol·L-1)were used under aerobic conditions at 25℃.Oxidative reactions of 3,5-DTBC (0.010 mmol·L-1～1.0 mmol·L-1)were initiated by the addition of the complex(0.010 mmol·L-1)in methanol-tris-HCl(tris=trihydroxymethylaminomethane,0.01 mol·L-1)buffer solution.The pH values of the reaction system changed in the range of 5～11.The absorbance versus wavelength(wavelength scan)of the solutions was recorded at a regular time interval of 5 min.A kinetictreatment on the basis of the Michaelis-Menten approach was applied and the results were evaluated from Lineweaver-Burk double-reciprocal plots.In each kinetic trial,8 points were recorded to obtain the kinetic data.The 3,5-DTBC solution in the absence ofthe complex was taken as a control.2.1 Crystal structure of complex 1In the crystal structure of complex 1(Fig.1),the asymmetric unit has two cobalt(Ⅱ)ions.One cobalt(Ⅱ)ion is five-coordinated by one chloride ionCl(1),two benzimidazole nitrogen atoms(N(2),N(4)),one carboxy oxygen atom O(1)and one amine nitrogen atom(N(1)) of the ligand LH,forming a distorted trigonal biyramid coordination geometry(angular structural parameter(τ) equals to 0.96)[16].Cl(1)and N(1)occupy the axial position,and N(2),N(4)and O(1)located in the equatorial plane.The Cl(1)-Co(1)-N(1)bonda ngle is 177.35(6)°,which is slightly deviated from ideal 180° (Table1).However，the other cobalt(Ⅱ)ion is partly coordinated by one water oxygen atom(O(5))(or one chloride ion Cl(2)),which is unusual for such complex. Similar example has also been reported for[Cu(4-atrz)4(Cl)0.5(H2O)0.5](ClO4)1.5with equal Cl/O ratio in the same position,and this may offer an opportunity to fine control over the Cl/O composition and properties for the complex[17].Since the Cl(2)is half occupancy,the ClO4-ion is located to balance the charge.N(6)and O(5)(or Cl(2))reside in the axial position,and N(7), N(9)and O(3)make up the equatorial plane.The Co-N bond distances range from 2.035(2)to2.320(2)nm, and the distance of Co-N(amino)is obviously longer than that of Co-N(benzimidazole),thus forming a distorted trigonal biyramidcoordination geometry(τ= 0.80).It′s also found that the carboxyl group is deprotonized,which leads to a single negative charge ligand L-.The dihedral angles between two benzimidazole rings of the deprotonized ligand L-in the unit cell are 56.68°and 56.01°,respectively.As shown in Table 2 and Fig.2,the uncoordinated anion ClO4-and water molecules participate in the formation of hydrogen bonds.The molecules are stabilized by intermolecular N-H…O,C-H…O and C-H…C l hydrogen bonds,leading to the formation of a three dimension network.2.2 Studies of catecholase activity3,5-DTBC has been widely chosen as a substrate in catecholase model complex studies.It′s readily oxidized to the corresponding 3,5-di-tert-butyl-oquinone(3,5-DTBQ)owing to its low redox potential, and its bulky substituents prevent further reactions such as ring opening[18].3,5-DTBQ is considerably stable and has a strong absorption at λmax=400 nm(ε= 1 900 L·mol-1·cm-1),so that the activity and reaction rate could be determined using UV spectroscopy[19]. Fig.3 showed the variation of the spectral behavior of complex 1(0.01 mmol·L-1)in the presence of 3,5-DTBC(100 equiv.)under aerobic conditions.The band that corresponded to 3,5-DTBQ was observed at 400 nm after addition of the substrate(3,5-DTBC)to the solution of complex 1.The kinetic studies on the oxidation of 3,5-DTBC were carried out by the method of initial rates.It′s found that the reaction between complex 1 and substrate(3,5-DTBC)was a first order reaction,so their relationship could be described using a formula: ln[(Af-Ai)/(Af-At)]=kt[20].Here,k is the rateconstant, Af,Aiand Atwere the final,initial and the time t absorbance of the reaction solution,respectively.The maximum absorbance of the growth of the quinone (3,5-DTBQ)at 400 nm was measured as a function of time,and Fig.4 showed a linear relationship in the ln[(Af-Ai)/(Af-At)]versus reaction time(t)plot in the presence of complex 1.The effect of the complexes (1～7)concentration on the oxidation of 3,5-DTBQ was also observed at pH 9.0 and 25℃(Fig.5).The reaction rate was initially increased linearly with increasing concentration of these complexes,indicating a firstorder dependence on each complex concentration.As shown in Fig.6,the pH dependence of the catecholase activity was promoted by the complexes(1～7)in the range of 5.0～11.0.The plots of v0(initial rate)vs pH value were observed to exhibit sigmoid-shape profiles, and the catalytic activities of all complexes were nearly increased in the pH value range from 7.0 to 9.0.The data depicted in Fig.7 revealed saturation kinetics of complex 1 with Michaelis-Menten-likebehavior.So an analysis based on the Michaelis-Menten model,originally developed for enzyme kinetics,was applied.The Michaelis-Menten equation is usually expressed as following:Here,vmaxis the maximum initial rate,Kmis Michaelis constant,kcatis the turnover number,namely,the amounts(mol)of substrate converted to product per minute per mole of mimetic enzyme.cSand cMare the concentrations of substrate and model complex, respectively.The Michaelis-Menten equation can be turned into Lineweaver-Burk equation by taking its double reciprocal:The inset in Fig.7 showed 1/v0was linear with 1/c3,5-DTBCfor complex 1,implying a first order reaction dependence.The slope of the straight line was Km/vmax, and the intercept on the vertical axis was 1/vmax. Several kinetic parameters vmax,Kmand kcatwere calculated from the Lineweaver-Burk plot model (Table 4).It is found that kcatof complex 1 toward 3,5-DTBC increased from 4.35 min-1(20℃)to 13.55 min-1(45℃).So the catalytic activity of complex 1 increased with increasing of temperatures.The kinetic data of the complexes(1～7)were also measured at pH 9.0 and 25℃.As shown in Table 5,the catalytic activity of these complexes were easily arranged in descending order:3＞7＞5＞1＞4＞2＞6.The catecholase model complexes have been reported to relate to several factors such as metal-metal distance,lability of exogenous ligands,coordination configuration and electrochemical properties[21].Of all the complex,3 showed the best catalytic activity,its difference with the other complexes(1,2,4,5,6)could be attributed to the redox potential effect of various metal ions on thecatecholasemodelcomplexes,and the results were in accordance with the literatures reported previously[11,22-23]. The catalytic activity of complex 7 was better than complex 1,because the former was adicobalt(Ⅱ)complex,which may be dependent upon the interaction between each active center and substrate due to its long dinuclear distance[11].A probable explanation for the catecholase catalytic reactivity of complex 1 was mainly related to its coordination environment.The five-coordinated cobalt(Ⅱ)ion has an unsaturated vacancy,and it could combine with the substrates[7,11].In summary,we have prepared a cobalt(Ⅱ)complex,which was characterized by single crystal X-ray diffraction.The complex showed pH value dependence for the oxidation of 3,5-DTBC in the range of 5～11,and the kinetics of 3,5-DTBC catalyzed by the complex obeyed the Michaelis-Mentent equation,its catecholase catalytic activity increased with the rise of the temperature.[1]Koval I A,Gamez P,Belle C,et al.Chem.Soc.Rev.,2006, 35:814-840[2]Klabunde T,Eicken C,Sacchettini J C,et al.Nat.Struct. Biol.,1998,5:1084-1090[3]Patra A,Giri G C,Sen T K,et al.Polyhedron,2014,67:495-504[4]Caglar S,Aydemir I E,Adiguzel E,et al.Inorg.Chim.Acta, 2013,408:131-138[5]Caglar S,Adiguzel E,Caglar B,et al.Inorg.Chim.Acta,2013, 397:101-109[6]Safaei E,Sheykhi H,Wojtczak A,et al.Polyhedron,2011, 30:1219-1224[7]ZHANG Yong(张勇),ZHOU Xia(周霞),HU Jia-Wei(胡家尾),et al.ChineseJ.Struct.Chem.(结构化学),2013,32(9): 1291-1296[8]Apurba B,Lakshmi K D,Michael G B D,et al.Inorg.Chem., 2012,51:7993-8001[9]CHEN Yan-Guo(陈彦国),LIAO Zhan-Ru(廖展如),LI Wu-Ke(李武客),et al.Acta Chim.Sinica(化学学报),2000,58 (10):1191-1195[10]Ogawa K,Nakata K,Ichikawa K.Chem.Lett.,1998,27:797-798[11]Zhang Y,Meng X G,Liao Z R,et al.J.Coord.Chem., 2009,62:876-885[12]SAINT,Program for Area Detector Absorption Correction, Siemens Analytical X-Ray Instruments Inc.,Madison,W I 53719,USA,1994-1996. [13]Sheldrick G M.SADABS,Program for Siemens Area Detector AbsorptionCorrection,University of Göttingen,Germany, 1996.[14]Sheldrick G M.SHELXS-97,Program for the Solution of Crystal Structures,University of Göttingen,Germany,1997.[15]Spek A L.Acta Crystallogr.,2009,D 65:148-155[16]Addison A W,Rao T N,Reedijk J,et al.J.Chem.Soc. Dalton Trans.,1984:1349-1356[17]Yi L,Du J Y,Liu S,et al.J.Chem.Res.,2004,1:29-31[18]Rompel A,Fischer H,Meiwes D,et al.FEBS Lett.,1999, 445:103-110[19]Seneque O,Campion M,Douziech B,et al.Eur.J.Inorg.Chem.,2002,8:2007-2014[20]Chen Z F,Liao Z R,Li D F,et al.J.Inorg.Biochem.,2004, 98:1315-1318[21]Neves A,Rossi L M,Bortoluzzi A J,et al.J.Braz.Chem. Soc.,2001,12:747-754[22]Qiu J H,Liao Z R,Meng X G.Polyhedron,2005,24:1617-1623[23]Lu L J,Song Y Y,Liu H,et al.J.Coord.Chem.,2012,65: 1278-1288。

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SYNTHESIS AND STRUCTURE DETERMINATION OF K2Ti6O13 NANOWIRESRuihong WANG1, Bolu WANG2, Qing CHEN2 and Lian-Mao PENG2,11Beijing Laboratory of Electron Microscopy, Institute of Physics, P.O. Box 603, Chinese Academy of Sciences, Beijing 10080, China2Department of Electronics, Peking University, Beijing 100871, ChinaNanoscale materials, such as nanotubes and nanowires, are among important advanced materials that are expected to exhibit unusually chemical and physical properties, which may be different from that of bulk materials. Among these nanoscale materials, titanate nanotubes and nanowires have many important applications in areas such as photo-catalyst, gas sensors, high energy cell and environmental purification[1-2]. Many methods have been developed to synthesize titanate whiskers[3], but typically the diameters of the products were in micron. In our previous work, titanate nanotubes and potassium titanate nanowires, both having diameter around 10nm, were synthesized using a simple one step hydrothermal reactionamong TiO2particles and alkali solution[4,5]. In this paper we report a successful synthesis of potassium titanate nanowires usinghydrothermal reaction among layered Na2Ti3O7and KOH solution.K 2Ti6O13nanowires were prepared in the following way: layerstructured Na2Ti3O7powder was added into a 10M KOH aqueous solution.The specimen was statically heated in a furnace at 200ºC for 24 hours. The final white product was filtered and washed with de-ionized water at room temperature. TEM sample was prepared by dispersing the powder in alcohol by ultrasonic treatment, dropping onto a holey carbon film supported on a copper grid, and then dried in air. TEM and EDX studies were carried out using Tecnai 20, and HREM using Tecnai F30. Image simulations were performed using the Cerius2 software.560Figure.1 is a low magnification TEM image showing many nanowires with diameters around 10 nm, and length around several hundreds nanometers. EDX was performed on isolated nanowires using nanoprobe mode on Tecnai 20. Figure 2 is a typical EDX spectrum, showing that there exist only K, Ti and O elements in the nanowires. Comparingwith the spectrum taken from K2Ti6O13nanowires made via reactionbetween TiO2and KOH we found that the atomic ratios in the present nanowires are the same, i.e. K:Ti:O = 2:6:13.Figure 3 shows a SAED pattern taken from an area containing manynanowires. The pattern can be indexed using K2Ti6O13structure. Theaxis of the nanowires is determined to be along the [010] direction using SAED analysis on isolated nanowires. The atomic structure of the nanowire was also investigated using HRTEM and image simulations. Experimental images were taken from nanowires along different zone axes. Figure 4 shows an experimental HREM image with an inserted simulated image. This image was taken along the [001] zone axis. The image was simulated for 300 keV primary beam, Cs=1.2mm and underfocus 50nm. The good agreement between the experimental andsimulated images confirms that the nanowire is indeed K2Ti6O13nanowire.Fig.1: Low magnification TEM image. Fig.2: A typical EDX spectrum from nanpowires.561562Fig. 3: SAED ring pattern taken from manynanowires. Fig. 4: Experimental HREM image taken along the [001] zone axis, with an insertedsimulated image.REFERENCES[1] G. Dagan, and M. Tomkiewicz, J. Phys. Chem. 97, 12651(1993).[2] A. Fujishima and K. Honda, Nature 238,37(1972).[3] J. K. Lee, K. H. Lee and H. Kim, J. Mater. Sci 31, 5493(1996).[4] Q. Chen, W. Zhou, G. H. Du and L. M. Peng, Adv. Mater., 14, 1208 (2002).[5] G. H. Du, Q. Chen, P. D. Han, Y. Yu and L. M. Peng, Phys. Rev. B, 67, 035323 (2003).[6] This work was supported by the Ministry of Science and Technology (Grant No001CB610502) and National Science Foundation of China (Grant Nos 90206021 and 60271004).Author introduction:Bolu.Wang, female, born in Chengdu, Sichuan, P.R.China onSept.11th , 1982. Entered Dept. Geographic Physics of PekingUniversity from Chendu Liewu Middle School in 2000. Transferred to Dept. Electronic Science as top 1 in the transferring exam in 2001. Study very hard and was chosen from over 120 students in Dept. Electronic Science to join the Chun-Tsung project lunched byprofessor T.D.Lee as a junior. Began research in the Center of Nanotechnology in Peking University in 2002 with the direction of Professor Qing.Chen. During the research process, received a lot of help from professor Qing.Chen, Dr.Shuang.Zhang, Dr.Ruihong.Wang and other group members. Already published a paper on Chemical PhysicsLetters and submitted a paper to the Proceedings of BCEIA2003.Further work is continuing.Sentiment:I have entered a very good group. My mentor didn’t ask me just to help other group members or wash cuvette in the lab. She encouraged me to read a lot of papers and to form my own ideas. It is she who tries to teach me to be creative. Thanks to her again here. Also, I would like to mention Dr.Shuang.Zhang, he does not avoid discussing with me just because I am still an undergraduate. During the discussion with him, I have learned a lot. I will never forget my precious days here.Mentor introduction:陈清，女，信息科学学院教授，博士生导师。

SYNTHESIS AND STRUCTURE DETERMINATION OF K2Ti6O13 NANOWIRES

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