配合物[Fe(CTS)2]·5SO4·7H2O的热分解动力学

研究了壳聚糖对Fe2+的吸附行为,并进行了条件优化,得到了较为理想的合成产物.通过红外光谱和紫外光谱进行了表征,进而用化学分析、元素分析确定了配合物的组成,并利用TG-DSC分析,采用常用的22种机理函数,对非等温动力学数据进行了线性回归拟合处理,求得了配合物主要分解阶段热动力学最可机理函数和动力学参数(E和A).     

配合物[Fe(CTS)_2]·SO_4·7H_2O的热分解动力学

研究了壳聚糖对Fe2 + 的吸附行为 ,并进行了条件优化 ,得到了较为理想的合成产物。通过红外光谱和紫外光谱进行了表征 ,进而用化学分析、元素分析确定了配合物的组成 ,并利用TG DSC分析 ,采用常用的 2 2种机理函数 ,对非等温动力学数据进行了线性回归拟合处理 ,求得了配合物主要分解阶段热动力学最可机理函数和动力学参数 (E和A)。     

NaHSO4·H2O催化合成苯甲酸甲酯

以NaHSO4*H2O催化苯甲酸与甲醇的酯化反应,合成了苯甲酸甲酯.研究结果表明,NaHSO4*H2O具有较高的催化活性.考察了苯甲酸/甲醇摩尔比、催化剂用量及反应时间对酯产率的影响.在优化反应条件[n(苯甲酸)∶n(甲醇)∶n(NaHSO4*H2O)=1∶2∶0.29,回流8h]下,苯甲酸甲酯产率达85.3%.     

新型镧三元配合物La(Glu)(Im)6(ClO4)3·4HClO4·4H2O的合成和热化学性质

合成了新型镧三元配合物La(Glu)(Im)6(ClO4)3·4HClO4·4H2O(Glu, 谷氨酸; Im, 咪唑). 用高精度全自动绝热量热仪测定了该配合物晶体80-390 K温区的热容, 利用实验热容数据, 建立了热容随温度变化的多项式方程; 根据焓、熵与热容的关系, 求出了配合物在80-390 K温区内相对于298.15 K的标准热力学函数(HT-H298.15)和(ST-S298.15). 绝热量热和差示扫描量热(DSC)分析均发现配合物在216和246 K附近存在玻璃态和晶型转变, 其机理可能是配合物中高氯酸根离子重取向运动. 用热重法(TG)检测了配合物的高温热稳定性并提出了可能的热分解机理.     

Sm（Val）C13·6H20低温热容及热化学性质

采用精密绝热量热计测定了稀土氨基酸配合物[Sm（Val）C13·6H2O]在80-376K温区的热容,从实验热容值计算出了热力学函数（HT-H298.15和ST-S298.15）。在308K附近,配合物的热容出现一个大的跳跃,可能是其玻璃化转变所致。对该配合物进行热重测试,得到了其可能的分解机理。     

稀土氨基酸配合物RE(Val)Cl3•6H2O(RE = Nd，Sm)的热分解动力学

合成了稀土氨基酸配合物晶体——三氯化缬氨酸六水合钕、钐，对合成样品进行了EDTA滴定、元素分析、红外光谱分析、热重、差热分析以及熔点测定，推测了配合物的热分解机理，采用Achar法和Coats-Redfern法研究了配合物热分解的非等温动力学过程，给出了各配合物样品失水阶段第一步反应和氨基酸骨架断裂阶段第一步反应的活化能（E）、指前因子的对数值（ln(A)）及热分解反应动力学方程式.     

Li(NTO)(H2O)2的热分解行为及其结构与性质的关系研究

摘要在水中合成了3-硝基-1,2,4．三唑-5-酮(NTO)的锂盐Li(NTO)(H2O)2,利用DSC,TG／DTG和IR方法研究了其金属配合物的热分解机理,并用Kissinger法、Ozawa法、积分法和微分法对标题配合物进行了非等温动力学研究,得到了热分解反应的动力学参数,确定了热分解第一阶段的动力学方程及配合物的热爆炸临界温度(Tb)为289．33℃．采取RHF／6-31G,DFT-RB3LYP／6-31G方法对标题化合物进行了几何全优化,并对其成键情况、电荷分布和化合物的稳定性进行了分析．     

配合物Ni（HDPC）2·3H2O和Cu（DPC）（H2DPC）·2H2O的制备及反应热动力学

吡啶-2,6-二甲酸（Pyridine-2,6-dicarboxylic acid,H2DPC）是一个灵活多变的刚性配体,能提供N原子和O原子与过渡、非过渡和稀土金属离子鳌合形成稳定的配合物,与过渡金属离子形成的配合物在催化、磁性、发光和医药等方面具有潜在的应用价值。H2DPC与Ni^2＋和Cu^2＋形成的配合物的晶体结构已有文献报道,但有关该类配合反应热动力学研究来见文献报道。本文用微量热法分别对NiCl2和CuCl2与H2DPC的液-液反应进行了热动力学研究。其结果可为这类配合物的反应机理研究和制备提供必要的技术参数。     

介质阻挡放电等离子体中·OH和HO2·自由基的数值模拟计算

在介质阻挡放电等离子体N2／O2／H2O／HCHO体系中通过解Boltzmann方程,得到电子能量分布函数,利用得到的电子能量分布函数计算电子。分子碰撞反应速率常数。然后把有关的反应速率常数带入速率方程,计算得到该体系在介质阻挡放电时,·OH、HO2·和电子的浓度随时间的演变以及·OH、HO2·浓度随H2O、O2摩尔分数的变化,并将模拟结果与实验值进行了对比,两者符合得较好。     

Intramolecular N-H···O and N-H···N hydrogen bonding patterns in N-benzyl and N-(pyridin-2-ylmethyl) benzamides

This Letter reports the evidences for intramolecular six-membered N-H···O hydrogen bonding in N-benzyl benzamides and five-membered N-H···N hydrogen bonding in N-(pyridin-2-ylmethyl) benzamide. Intramolecular six-membered N-H···X (X = O or F) hydrogen bonding in 2-methoxyl- or 2-fluorobenzamides is used to lock the amide proton from forming strong intermolecular N-H···OC hydrogen bonding. As a result, for the first time the new intramolecular hydrogen bonding patterns are observed in the crystal structures of nine amides, whereas the whole molecules give rise to a new class of three-center hydrogen bonding motif. ¹H NMR study in chloroform-d also supports that this weak intramolecular hydrogen bonding pattern exists in solution.     

Phencyclone Diels-Alder adducts as a new crystalline host. Role of CH···π and CH···O interactions

A series of crystalline host compounds, which have a bicyclo[2.2.1]heptene-7-one system, has been synthesized and their inclusion behavior has been investigated. The cycloadduct of phencyclone and N-naphthylmaleimide forms a 1:1 crystalline inclusion complex with 2-butanone. The crystal structure indicates the presence of weak lattice forces supported by CH···π and CH···O interactions.     

Structures and Electronic Properties of HOCl···HCOCl Complexes

B3LYP/6-311++G** and MP2/6-311++G** calculations were used to analyze the interaction between hypochlorous acid (HOCl) and formyl chloride (HCOCl). The results showed that there were four equilibrium geometries (S1, S2, S3, and S4) optimized at B3LYP/6-311++G** level, and all the equilibrium geometries were confirmed to be in stable states by analytical frequency calculations. Complexes S1 and S3 use the 5H atom of HOCl as proton donor and the terminal 1O atom of HCOCl as acceptor to form red shift hydrogen bond systems. However, the blue-shifted hydrogen bond (2C-3H···6O) coexists with 4Cl···5O interaction in structures S2. As for S4, it uses the 7Cl atom of HOCl as proton donor and the terminal 1O atom of HCOCl as acceptor to form red shift halogen bond system. Interaction energies between monomers in the four complexes corrected with basis set superposition error (BSSE) and zero-point vibrational energy (ZPVE) lie in the range from −5.05 to −14.76 kJ·mol⁻¹ at MP2/6-311++G** level. The natural bond orbital (NBO) and atoms in molecules (AIM) theories have also been applied to explain the structures and the properties of the complexes.     

对自旋交叉化合物[Fe(dpq)(py)2(NCS)2]·H2O·py和[Fe(dpq)(py)2(NCSe)2]·1.5H2O的研究

为了研究配体修饰对自旋交叉现象的影响,我们合成了两个Fe(Ⅱ)自旋交叉的配合物[Fe(dpq)(py)₂(NCS)₂]·H₂O·py和[Fe(dpq)(py)₂(NCSe)₂]·1.5H₂O,(dpq=二吡嗪[2,3-f:2′3′-h]喹喔啉,py=吡啶)。通过对这两个配合物磁性质和穆斯堡尔谱的研究,发现和用邻啡咯啉配体合成的配合物比较,配体的修饰对自旋交叉性质以及其临界温度     

一个半水合和五水合醋酸镧的脱水过程及脱水焓测定

醋酸镧已报道三种水合物:LaAc₃·1.5H₂O(Ⅰ)^[1,2]、LaAc₃·5H₂O(Ⅱ)^[3]和LaAc₃·H₂O(Ⅲ)^[4],迄今尚未见(Ⅰ)和(Ⅱ)的脱水焓数据发表,我们继(Ⅲ)的研究工作后,采用新的合成方法制得了(Ⅰ)和(Ⅱ),并采用DTA-TG-DTG联用技术和DSC技术分别对这两种水合物进行了脱水过程及脱水焓的测定。测得(Ⅰ)和(Ⅱ)的脱水过程分别为:     

Tris(Znsalen) cryptand minimizes Znsalen aggregation arising from intermolecular Zn…O interaction

Exploring the factors to control Znsalen aggregation is of importance to design functional materials in catalysis, optical materials and biological imaging. In this work, we synthesized and characterized four cryptand type triZnsalen complexes and found that cryptand structure could efficiently minimize intermolecular Zn···O interaction. More importantly, encapsulated by PLGA nanoparticles, cryptand triZnsalen 1 displayed visible intracellular fluorescence whereas monomeric Znsalen 5 could not. These results provide a new access to design new luminescent materials with the potential application in optics and biological studies.     

Molecular Structure and Properties of a Novel Acylhydrazone (C14H14O6N4)·HCON(CH3)2·2H2O

[N-(Propionic acid)] terephthalal acyl dihydrazone(H₄L) was synthesized and characterized by element analysis, IR, ¹H NMR and MS. The theoretical studies on H₄L were carried out at HF/6-31+G(d) and B3LYP/ 6-31+G(d) levels. The main decomposition stage of it was studied with IR track. The kinetic parameters[the apparent activation energy(E_a) and pre-exponential constant(A) of the first and second stages of decomposition reaction] were obtained by Kissinger and Ozawa’s methods. Furthermore, the antimicrobial activity of H₄L against wheat rust was investigated by spore sprout method.     

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using -C-H···O supramolecular synthon

Mono and doubly alkynyl substituted ferrocene complexes, [Fc(CH₂OCH₂CCH)_n], 2-3 (2: n = 1; 3: n = 2; Fc = ferrocene) have been synthesized from the room temperature reaction of mono and 1,1′-dihydroxymethyl ferrocene, Fc(CH₂OH)_n , 1a-b (1a: n = 1; 1b: n = 2) and propargyl bromide, in modest to good yields. These new ferrocene derivatives have been characterized by mass, IR, ¹H, ¹³C NMR spectroscopy, and molecular structures of compound 2 and 3 were unequivocally established by single crystal X-ray diffraction study. The crystal structure analysis revealed that 2 and 3 consist of infinite 1D zig-zag hydrogen bonded chains and 2D microporous hydrogen bonded network of molecules, linked by intermolecular C-H···O hydrogen bonding. The molecular structures of both 2 and 3 are further stabilized by C-H···π interactions.