锌(Ⅱ)配合物的超分子设计及对甲醇蒸气的吸附性能

采用饱和蒸气扩散技术, 将2,4-二羟基苯甲醛缩异烟酰腙(H₂dhbi)配体分别与Zn(ClO₄)₂·6H₂O和Zn(NO₃)₂·6H₂O进行配位作用, 得到2种不同配位模式的金属-有机框架材料[(dhbi)₂Zn₂·8H₂O]_n(1)和{[(dhbi)₂(H₂O)₂Zn₂]·4DMF]}_n(2). 利用X射线单晶衍射、 热分析技术(TG-DTA)和X射线粉末衍射(PXRD)等方法进行了结构表征. 进一步将配位聚合物1和2用于对甲醇分子的吸附性能研究, 结果表明, 化合物1是一种理想的微孔材料, 其对甲醇分子的吸附能力为化合物2的近5倍, 采用PLATON对材料的孔隙体积进行计算得到化合物1和2的孔隙率分别为38.2%和5.5%.     

对苯二甲酸根桥联的双铜(Ⅱ)和双锰(Ⅱ)配合物的合成和长程磁交换作用

合成和表征了4种新型配合物[Cu₂(TPHA)(NO₂-Phen)₁](ClO₁)₂·H₂O、[Cu₂(TPHA)(Me-bpy)₁](ClO₁)₂、[Mn₂(TPHA)(NO₂-Phen)₁](ClO₁)₂·2H₂O和[Mn₂(TPHA)(Me-bpy)₁](ClO₁)₂(TPHA:对苯二甲酸根阴离子;NO₂-Phen:5-硝基-1,10-菲绕啉;Me-bpy:4,4'-二甲基-2,2'-联吡啶).测定了配合物的变温磁化率,并求出了交换积分J分别为-5.04、-6.52、-0.68及-0.73cm^-1.     

基于超分子构筑模块和酰胺插入的螺旋配体的PCN类型金属有机骨架的结构和选择性吸附CO2

首次实现了窗口缩小的小斜方六面体超分子构筑模块(SBB)和酰胺功能化螺旋配体5,5′-(((1,1′-biphenyl)-2,2′-dicarbonyl)bis(azanediyl))diisophthalic acid(H₄L)的链接,形成了一个pcu拓扑的微孔金属有机骨架[Cu₂(L)(H₂O)₂]·DMF·6H₂O(NTUniv-53),其在室温下展示了良好的二氧化碳吸附选择性。由于窗口缩小和酰胺的共同作用,该选择性基本不受温度变化的影响。     

Preparation and characterization of a novel single crystal of Th(IV) with cucurbit[6]uril

One new single crystal [Th(NO₃)₂(H₂O)₆](CB₆)(NO₃)2·2H₂O was prepared using Th(NO₃)4·4H₂O and cucurbit[6]uril (CB₆) as reagents in HNO₃ aqueous solution by slow evaporation. The coordination number of Th⁴⁺ is ten. Th⁴⁺ is coordinated with six monodentate water molecules and two symmetric bidentate chelating nitrate ions, while other two nitrate ions act as the counterion anions. CB₆ is a second-sphere ligand which is hydrogen bonded to the water molecules of [Th(NO₃)₂(H₂O)₆]²⁺. Besides, there are also two free water molecules in the crystal system.     

体系Mg(NO3)2-MgCl2-H2O作为相变储能材料的相图预测

应用修正的BET热力学模型对Mg(NO₃)₂-MgCl₂-H₂O体系在273～373 K的相图进行预测, 发现两个共晶点, 并通过实验对共晶点组成材料的吸热和放热行为进行测定, 发现三元共晶点Mg(NO₃)₂•6H₂O(45.6%)-Mg(NO₃)₂•2H₂O (29.6%)-MgCl₂•6H₂O(24.8%)储能效果较差, 而二元共晶点Mg(NO₃)₂•6H₂O(61.6%)-MgCl₂•6H₂O(38.4%)在熔点附近具有很好的储放热能力, 其相变热焓经差热分析为136.8 J•g^－1, 说明该材料可用作潜在的相变储能材料.     

三元体系MgCl2-CO(NH2)2-H2O在25℃时的等温溶度与新相研究

测定了25℃时三元体系MgCl₂-CO(NH₂)₂-H₂O的等温溶度及饱和溶液的折光率和密度,且绘制成溶度图和性质-组成图.在三元体系内形成2个三元化合物新相:MgCl₂·CO(NH₂)₂·4H₂O(记作A)和Mgcl₂·4CO(NH₂)₂·2H₂O(记作B),B为新化合物.三元体系的溶度图由4支单饱和线[对应单饱和固相为MgCl₂·6H₂O、三元化合物A和B、CO(NH₂)₂]组成,这4支单饱和线两两交于3个三元无变点[对应双饱和固相为MgCl₂·6H₂O+A、A+B、B+CO(NH₂)₂].     

An efficient and versatile synthesis of aromatic nitriles from aldehydes

A simple and direct method has been developed for synthesis of nitriles based on one-pot reaction of aromatic aldehydes with three different kind of reagents:CeCl₃7H₂O/KI/H₂O₂,CeCl₃·7H₂O/KI/UHP and（NH₄）₂Ce（NO₃）₆/KI/H₂O₂ in aqueous ammonia.     

三维Cu-MOF对亚甲蓝的吸附和光催化降解及其机理

本文报道了[Cu₃(ppda)₃(tib)₂(H₂O)₄]·6H₂O(Cu-MOF)的合成、结构、吸附和光催化降解性能。在Cu-MOF中,1,4-苯二乙酸(H₂ppda)和1,3,5-三(1-咪唑基)苯(tib)配体交替连接Cu离子形成二维层,层与层之间通过trans-ppda^2-相互穿插形成稳定的三维结构。Cu-MOF对亚甲蓝(MB)的催化效率为97%,最高反应速率常数为0.019 7 min^-1。光催化降解机理：在光的激发下,催化剂表面的光生电子和空穴对发生分离,并与O₂、H₂O、H₂O₂反应生成活性物质,将染料降解为CO₂和H₂O。在MB溶液中加入NaCl(200 g·L^-1)后,Cu-MOF的吸附量有所提升(87.23 mg·g     

基于Keggin型杂多酸的无机-有机杂化物的合成和光催化活性

采用水热合成方法制备了2个基于Keggin型杂多酸的无机-有机杂化物, 化学式分别为{[Cu₂(4,4′- bipy)₄(H₂O)₄](SiMo₁₂O₄₀)·18H₂O}_n(1)和{[Cu₂(4,4′-bipy)₄(H₂O)₄](PMo₆W₆O₄₀)·18H₂O}_n(2)(bipy=bipyridine). 结构分析 表明2个化合物同构, Cu²⁺是六配位, 分别与4个4,4′-bipy上的N原子和2个水分子上的O原子结合, 形成 [Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺二维层状结构. 杂多阴离子通过静电与配位阳离子[Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺作用交叉排列在层间. 通过红外光谱、 粉末X射线衍射和固体紫外-可见漫反射光谱等对化合物的性质进行了表征. 研究了所合成化合物对水溶性染料亚甲基蓝的降解活性, 发现2种化合物对于亚甲基蓝均表现出显著的光降解活性, 并对它们的催化机理进行了讨论.     

稀土冠醚类配合物的研究(Ⅺ)——硝酸钪、钇与二苯并-24-冠-8的固态配合物的合成及性质

以无水乙腈为反应介质,合成了硝酸钪及硝酸钇与DB24C8的固态配合物,确定其组成为Sc(NO₃)₃·DB24C8·2H₂O和[Y(NO₃)₃]₄·(DB24C8)₃·8H₂O,并对冠醚及其配合物的某些性质进行了对比研究。     

Syntheses and X-ray crystal structures of [Co(η-CO3)(NH3)4](NO3)·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O

[Co(η²-CO₃)(NH₃)₄](NO₃)·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O were prepared by prolonged aerial oxidation of a solution of Co(NO₃)₂·6H₂O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η²-CO₃)(NH₃)₄][NO₃]·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O reveal a monomeric octahedral cobalt center with η²-bound CO₃²⁻ in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH⁻ and one μ₂-CO₃²⁻ groups with three terminal NH₃ ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident.     

Synthesis and X-ray crystal structures of bis(bis(μ2-2-aminoethanolato–N,O,O)–cobalt(III))–cobalt(II) hydrate, tris(biscyclohexylammonium)μ-hydroxo–bis(μ2-nitro–N,O)–hexanitro–dicobaltate(III) and biscyclohexylammonium nitrate(III)

Two new cobalt complexes: Co₃(NO₂)₄(NH₂CH₂CH₂O)₄·H₂O (1) and (NH₂(C₆H₁₁)₂)₃[Co₂(NO₂)₈OH]·3H₂O (2) and the compound (NH₂(C₆H₁₁)₂)NO₂ (3) were synthesised and their structures have been determined using single-crystal X-ray diffraction. Compound 1 consists of two centrosymmetrical trinuclear complexes and a water molecule of crystallization. Ligands coordinated to Co atoms are nitro and aminoethanolato groups. Structure 2 is built up of biscyclohexylammonium cations, dinuclear anions with hydroxo and nitro groups coordinated to Co atoms and water molecules. The coordination of Co atoms in both structures is roughly octahedral.     

DFT and TD-DFT investigation of the ground and excited states for dinuclear and mononuclear copper(I) and silver(I) complexes of 3,5-bis(trifluoromethyl)pyrazole and related bis(pyrazolyl)borate

The ground-state and low-lying excited electronic states in mononuclear, {H₂B[3,5-(CF₃)₂Pz]₂M(2,4,6-Cn)} (M₁) and dinuclear {[3,5-(CF₃)₂Pz]M(2,4,6-Cn)}₂, (M₂) (Pz = pyrazole, Cn = collidine and M = Cu, Ag), are studied using DFT approach. Electronic properties are calculated using B3LYP, while excited singlet and triplet-states are examined using TD-B3LYP. All the calculated low-lying transitions are categorized as ¹MLCT transitions. A good agreement was found between experimental spectra and predicted emission wavelengths (λ_em), the corresponding emissive states being assigned as ³MLCT for Cu₁ and Ag₂, ³MLLCT for Ag₁ and ³LLCT for Cu₂.     

LaCoO3对H2S选择氧化性能的影响

使用溶胶-凝胶法制备了LaCoO₃催化剂,采用XRD、BET和XPS等方式对催化剂进行了表征,考察了该催化剂制备过程中煅烧温度、表面活性剂PEG-6000和PEG-20000含量对其H₂S选择氧化制硫磺反应催化活性的影响。结果表明,表面活性剂PEG-6000及PEG-20000的添加能明显提高LaCoO₃的催化活性。0.02 mol La（NO₃）₃+0.02mol Co（NO₃）₂溶液中添加0.30 g PEG-20000、煅烧温度为650℃时所制备的LaCoO₃催化活性最好;在最佳反应温度260℃下,H₂S的转化率达到96.10%,硫选择性为93.77%。     

铈源对甲醇水蒸气重整制氢CuO/CeO2催化剂的影响

采用沉淀法合成了CeO_2载体,再经浸渍法负载活性组分得到CuO/CeO_2催化材料,探究了铈源(Ce(NO_3)_3·6H_2O、Ce Cl_3·6H_2O、Ce(NH_4)_2(NO_3)_6、Ce(SO_4)_2·4H_2O)对CuO/CeO_2催化性能的影响。通过采用XRD、SEM、N_2O滴定、BET和H_2-TPR等表征手段对催化材料的结构和性质研究发现,四种铈源合成的CuO/CeO_2催化材料在Cu比表面积、还原性能以及活性组分和载体间的相互作用方面存在着明显差别。其中,由Ce(NO_3)_3·6H_2O合成的CuO/CeO_2催化材料的Cu比表面积较大,CuO还原温度较低,CeO_2载体与CuO之间相互作用较强,在甲醇水蒸气重整反应过程中,表现出较佳的催化活性,在反应温度为553 K,水醇比n(H_2O)/n(MeOH)为1.2,甲醇水蒸气气体空速(GHSV)为1760 h~(-1)时,甲醇的转化率为100%,重整气中CO摩尔含量为0.84%。     

Controlling structural topology of metal-organic frameworks with a desymmetric 4-connected ligand through the design of metal-containing nodes

Two new metal-organic frameworks(MOFs),[Cu2(H_2O)_2(BCPIA)](BUT-20)and(Me_2NH_2)[In(BCPIA)](BUT-21)were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand,5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid(H_4BCPIA)and Cu(NO_3)2 2.5H_2O or In(NO_3)_3·5H_2O,respectively,and characterized by single-crystal and powder Xray diffraction,thermogravimetric analysis,infrared spectroscopy,and elemental analysis.The two MOFs have three-dimensional structures,in which both the BCPIA 4 ligand and metal-containing entities,Cu_2(COO)_4(H_2O)_2 and In(COO)_4 act as 4-connected nodes.However,different linkage configurations of the two metal-containing nodes,quadrilateral Cu_2_TD_2(COO)_4(H_2O)_2and tetrahedral In(COO)_4,lead to distinct structural networks of BUT-20 and 21,with Nbo and Unc topologies,respectively.     

氨基修饰的金属有机框架Cu_3(BTC)_2的制备及其CO_2吸附性能研究

首先制备了嫁接氨基的均苯三甲酸,同时以其为原料通过溶剂热法合成了金属有机框架材料Cu_3(NH_2BTC)_2,利用XRD、N_2吸附-脱附、热重、红外、原位红外分析等表征手段对吸附剂进行了表征,并通过固定床测量穿透曲线的方法研究其CO_2吸附性能。结果表明,氨基被成功引入Cu_3(BTC)_2骨架中。氨基修饰的Cu_3(BTC)_2对CO_2有着较高的吸附容量,在10 kPa,50℃的条件下CO_2吸附量为1.41 mmol/g,这源于材料对于CO_2同时存在着物理吸附和化学吸附。     

孔隙结构可调的Cu2O球状纳米结构及其NO2气体传感性质

报道在聚乙烯吡咯烷酮(PVP)的协助作用下,通过简单调节OH^-离子的浓度及Cu²⁺的释放速度,将Cu₂O调节为具有不同空腔特征(介孔、空心及实心)结构的纳米球.研究表明, OH^-根离子的扩散动力学是决定产物结构的关键因素.当[OH^-] > 0.05 mol·L^-1时,高的化学势使其迅速扩散到PVP胶团内部,与吸附在PVP链上的Cu²⁺反应形成Cu(OH)₂,在抗坏血酸(Vc)的还原作用下经过重结晶得到Cu₂O实心球纳米结构;当[OH^-] < 0.025 mol·L^-1时,其扩散速度下降,首先与吸附在PVP胶团外部的Cu²⁺反应形成Cu(OH)₂, Cu(OH)₂的形成阻碍了OH^-离子的向内扩散,形成具有较大空腔(~220 nm)的空心球;当0.025 mol·L^-1 < [OH^-] < 0.05 mol·L^-1时,形成较小空腔(30-60 nm)的空心球.以NH₃水为OH^-缓释源时,虽然OH^-浓度较低,但同时Cu²⁺的浓度也低,胶团外部形成的Cu(OH)₂不足以阻碍OH^-离子的向内扩散,反应过程中NH₃的释放及较低的OH^-浓度阻碍了重结晶的发生,从而形成Cu₂O介孔纳米球.对三种典型结构特征的产物进行了NO₂气体传感性质研究,结果表明, Cu₂O介孔纳米球相比空心结构和实心结构具有更为优异的响应性.结合比表面积数据,我们认为介孔纳米球疏散的结构有利于NO₂气体的扩散和O₂的吸附,从而表现出了更灵敏的气体传感性.     

THE ACTION MODE OF CISPLATIN ON DNA-SYNTHESIS AND CHARACTERIZATION OF N7 N1 CROSS-LINKAGE MODEL COMPOUND OF PLATINUM AND GUANOSINE

The title Pt-Guo compound was synthesized and isolated by the reaction between cis-[Pt(NH3)2(H2O)2](NO3)2 and guanosine of mol ratio1:1 in a neutral aqueous solution followed by careful purification with partial crystalization and recrystallizatlon from water at 0℃.The compound was characterized by elemental analysis,molecular weight determination,DTA,and C NMR spectroscopy and its formulawas found to be [8(GuoH-1)7 (OH)2] (NO3)7 8H2O.The isolation of the compound provides direct evidence for the intrastrand cross-linkage between cisplatin and DNA through N7,N1 atoms of two adjacent guanines.