Synthesis and photophysical and electrochemical properties of new cyclometalated platinum complex containing oxadiazole ligand

A new cyclometalated platinum complex containing 2, 5-bis（naphthalene-1-yl）-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry （CV） analysis shows that the EHOMO （energy level of the highest occupied molecular orbital） and ELUMO （energy level of the lowest unoccupied molecular orbital） of the platinum complex are about -5.69 and -3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.     

大环与多吡啶混配稀土三元配合物的合成与性质

Robson大环希夫碱配合物通常以金属离子为模板一步合成得到,获得了大量发展和广泛应用.为进一步拓展混配的大环希夫碱配合物体系并研究其特殊性质和用途,以三价铽离子为模板离子,用2,6-二甲酰基-4-甲基苯酚和2-羟基-1,3-丙二胺进行[2+2]模板缩合反应,并在反应条件下加入取代的三联吡啶配体一步法直接合成了一个新型的大环与三联吡啶混配单核稀土铽配合物,用红外光谱和电喷雾质谱等物理方法进行了结构表征.电喷雾质谱研究表明:配合物为[2+2]缩合反应生成的单核结构并存在大环配体和三联吡啶混配的结构单元.凝胶电泳实验和抗菌实验证明了目标配合物对质粒DNA p BR322具有一定的切割活性,同时对大肠杆菌也有一定的抑制作用.     

含苯并杂环的分子扭曲型材料的合成及其发光性能

在电子传输发光单元(1,8-萘酰亚胺)中引入空穴传输单元(苯并噻唑、苯并噁唑、苯并咪唑),采用分子扭曲设计,合成了9个具有分子扭曲构型的萘酰亚胺衍生物,并对其电化学性能、光谱性能和热稳定性能进行了测试.所合成的衍生物具有较高的量子产率和很好的热稳定性,荧光寿命在10 ns左右,呈黄绿光,可作为发光材料应用在有机电致发光器件中.     

稀土Eu对发光玻璃白光发射的调控

用高温熔融法制备了Eu2O3单掺和Ce/Tb/Eu三元共掺杂的CaO-B2O3-SiO2(CBS)发光玻璃材料,并使用荧光分光光度计和CIE色度坐标对其结构以及发光特性进行了研究.光谱分析结果表明:在394nm激发下,Eu2O3单掺杂的CBS发光玻璃的发射光谱中出现了Eu3+的特征发射峰.这些发射峰主要起源于Eu3+中的4f电子的f-f跃迁;在374nm激发下,三元共掺杂发光玻璃的发射光谱中同时观测到了起源于Ce3+、Tb3+和Eu3+的蓝色、绿色和红色的三基色发射,这些发射可进一步混合成为白光发射.此外,Ce/Tb/Eu三元共掺杂发光玻璃的发光颜色,随着Eu2O3含量的增加从蓝光逐渐过渡到白光,这显示出了发光颜色的可调节性,极大地扩展了其在白光发光领域中的应用.     

三脚架型配体、配合物的合成及荧光性质

为了进一步研究配体结构对稀土离子配位行为的影响,合成了以N为中心的三足配体——2,2′,2″-三（2-苯胺基甲酰基苯氧基）三乙胺（L）及其稀土硝酸盐配合物．试验表明,在合成三（2-氯乙基）胺盐酸盐时,应先用适当的溶剂（如苯）溶解三乙醇胺盐酸盐,然后向其中缓慢滴加氯化亚砜,并在合成N-苯基水杨酰胺的过程中,用DCC作脱水剂,效果较好．该合成方法明显降低了氯化亚砜的挥发,减少了原料损失,使操作条件更温和。收率可达80％以上：在室温下．铽配合物表现出Tb^3＋的特征荧光发射峰．     

Synthesis and fluorescence properties of Tb(Ⅲ) complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)-vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.     

Schiff碱双冠醚及其多核配合物的合成和表征

合成了Schiff碱双冠醚配体N,N′-二[(4′-苯并15冠5)次甲基]三乙烯四胺(L)及其稀土—镍硝酸盐配合物Ln3Ni(NO3)11·L(Ln=La,Ce,Pr,Eu,Gd,Y).元素分析、摩尔电导、红外光谱、紫外光谱等分析结果表明:配合物的组成为Ln3Ni(NO3)11·L·nCH3CN(n=0,1),属于1∶1型大阴大阳离子缔合物.配合物中,镍离子与桥链上的四个氮原子配位,其中两个稀土离子分别与冠醚环上的氧原子及硝酸根离子配位形成大阳离子,另一稀土离子与硝酸根离子配位形成阴离子.     

Synthesis and fluorescence properties of Tb（Ⅲ） complexes with pyridine-2,6-dicarboxylic acid derivatives

Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid （4-SPDA） and 4-（4-（2-（2, 6-dicarboxypyridin-4-yl）- vinyl）styryl）pyridine-2,6-dicarboxylic acid（DSPDA） and their complexes with Tb（Ⅲ） were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb（Ⅲ） are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution （pH=7）, and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands （4-APDA and DSPDA） are the good sensitizers for Tb（Ⅲ） ion.     

Effect of B2O3 on the Structure and Photoluminescence Properties of Sol-gel Glass Doped with Terbium Organic Complex

Both silica and boron-silica glass materials doped with terbium organic complex were prepared by in situ sol-gel method respectively. XRD and SEM measurements were performed to verify the non-crystalline structure of the glass. The influence of the glass contents on the structure of the glass and the erwrgy level of the doped Tb （Ⅲ） ions was analyzed by the emission spectra and IR spectra. The effect of B2O3 on the photolumirwscence properties of rare earth organic complex in silica- based glass was investigated. The IR spectra indicate that the in situ sylthesized rare earth complex molecule was confined to the micropores of the bost and the vibration of the ligands was frozen. When B2O3 was added into the silica host gel, B2O3 had little influence on the noncrystallirw structure of the glass, and BO3 triangle, which had a layer structure different from the silica framework, could form. So the silica network became more inhomogenous, and the luminescence of terbium complexes was quenched with the increase of the B2O23 amount.     

Electrorheological fluid of kaolinite-based ternary nanocomposite and its properties

Electrorheological fluids (ERFs) are typical suspensions composed of micrometer size particles and dielectric liquids[1―3]. The ER response produces an instantaneous and reversible change in rheological properties of a suspension when being exposed to an electric field normal to the flow direction. The material parameters of ERF such as vis-cosity, yield stress, and shear modulus can change obviously and reversibly upon the application of an external electric field. These characteristics f…     

酰基吡唑啉酮缩氨基硫脲V(Ⅳ)Fe(Ⅲ)配合物的合成与表征

合成了含硫席夫碱试剂 1-苯基 - 3-甲基 - 4 - (α -呋喃甲酰基 )吡唑啉酮 - 5缩氨基硫脲 (HL)及其钒、铁的配合物 .元素分析及摩尔电导值表明新配合物的组成为 [VOLCl]·C2 H5OH和 [FeL2 ]Cl·0 .5C2 H5OH .用红外光谱、紫外光谱、差热 -热重对配合物进行了表征     

NaEuF_4微米晶的水热合成与表征

以柠檬酸钠(Na3Cit)为螯合剂和形貌控制剂,通过水热方法成功合成了尺寸均匀的六角形NaEuF4微米晶.采用X-射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能量色散X射线(EDX)和光致发光光谱(PL)对所得产物的结构、形貌以及发光性质进行分析.XRD和SEM分析表明:所得NaEuF4微米晶为六方相,颗粒较均匀.NaEuF4微米晶的尺寸和形貌可通过改变Na3Cit的量和反应时间进行调整.提出NaEuF4微米晶的可能形成机理,并研究其光致发光光谱性质.     

九钨二钼镓杂多酸盐的合成及性质

报道了二钼取代钨的１１系列杂多配合物的合成方法，首次合成了５种通式为ＭａＨｂ〔ＧａＷ９Ｍｏ２Ｏ３９〕·ｎＨ２Ｏ（Ｍ＝Ｎａ＋，Ｋ＋，ＮＨ＋４，Ｍｅ４Ｎ＋，Ｅｔ４Ｎ＋ａ＋ｂ＝９）的盐，采用ＩＲ、ＵＶ、Ｘ射线粉末衍射等方法对化合物进行了表征，元素分析结果表明标题化合物为Ｋｅｇｇｉｎ结构的１１系列杂多配合物。     

三元复数的指数形式及相关性质探讨

三元复数是作者新近提出的一种“超复数”．文中先将三元复数表记成简洁直观的复指数形式，在此基础上接着讨论了三元复数的基本性质，然后再制定复指数形式的三元复数旋转积的运算规则．指出使用旋转积的概念可用于表达矢量的旋转，旋转的结果是可以形成柱面、锥面、球面等复杂的空间回转曲面．此外三元复数还可作为描述物体复杂空间运动的数学工具．     

Synthesis and electrochemical properties of polyradical cathode material for lithium second batteries

A stable polyradical, poly (2 ,2,6,6-tetramethylpiperidinyloxy methacrylate)(PTMA) , was synthesized, and its structure was determined by infrared, ultraviolet-visible, and ESR spectroscopy. Cyclic voltammograms of the PTMA polyradical electrodes were obtained by using a three-electrode cell at a scan rate of 5 mV/s within a potential range of 3. 2-4. 0 V. The results show that the shape of oxidation peak is very similar to that of reduction peak, and oxidation peak current is equal to the corresponding reduction peak current, which suggest that PTMA possesses an excellent reversibility. The difference of the anodic peak potential (Ea,p = 3. 66 V, vs Li/Li+) and ca-thodic peak potential(Ec,p = 3. 58 V, vs Li/Li+ ) is estimated at 80 mV, which is extremely less than that of the other organic positive materials in lithium second batteries such as organosulfide compounds, leading to a capability for high current capability in the charging and discharging process of the battery. The maximum discharge specif     

铟-二乙三胺五乙酸配合物的合成与表征

以二乙三胺五乙酸(dtpa)为配体合成含有自由羧酸基的稀散金属离子InⅢ配合物,分子式为K[ InⅢ(Hdtpa)]·3.5 H2O.[InⅢ(Hdtpa)]-配离子中InⅢ与来自同一个二乙三胺五乙酸的三个氮原子和四个氧原子构成七配位面冠三方柱体结构.其中[ InⅢ(Hdtpa)]-配离子提供一个可用于修饰的未参与配位的自由羧酸基(-CH2COOH),配合物通过修饰与具有定向功能的生物大分子相接可形成定向放射性抗肿瘤药物.     

2，5-二羟基-1，4-苯醌阴离子桥联配合物的合成与表征

在水和乙醇混合溶剂中,用2,5-二羟基-1,4-苯醌阴离子(DHBQ)为桥配体,首次合成了Mn(Ⅱ)、Cu(Ⅱ)的桥联配合物,通过元素分析、差热-热重分析及红外光谱研究,可以确定两种配合物都应具有链状结构,组成分别为[Mn(μ-DHBQ)(H2O)2]n和[Cu(μ-DHBQ)H2O]n。     

双臂大环稀土配合物的合成及其生物活性

为进一步发展新型Robson大环配合物体系,在三价铒离子的存在下,用2,6-二甲酰基-4-甲基苯酚和三(3-氨基丙基)胺(trpn)通过[2+2]模板缩合反应直接合成了一个新型的双臂大环单核稀土铒配合物,通过物理方法对其进行了结构表征,用凝胶电泳实验和抗菌实验初步考察了配合物的生物活性.电喷雾质谱研究表明:配合物为[2+2]缩合反应生成的单核结构.凝胶电泳实验研究表明:标题配合物能将DNA切割成环形缺刻型DNA,并以插入方式与相DNA结合;同时抑菌毒性实验证实了配合物对大肠杆菌也有一定的抑制作用.     

Mechanical,electrical, and thermal properties of the directionally solidified Bi-Zn-AI ternary eutectic alloy

A Bi-2.0Zn-0.2A1 （wt%） ternary eutectic alloy was prepared using a vacuum melting furnace and a casting furnace. The samples were directionally solidified upwards at a constant growth rate （V= 18.4 μm/s） under different temperature gradients （G = 1.15-3.44 K/mm） and at a constant temperature gradient （G = 2.66 K/mm） under different growth rates （V= 8.3-500 μm/s） in a Bridgman-type directional so- lidification furnace. The dependence ofmicrostructure parameter （2） on the solidification parameters （G and V） and that of the microhardness （Hv） on the microstructure and solidification parameters were investigated. The resistivity （ρ） measurements of the studied alloy were per- formed using the standard four-point-probe method, and the temperature coefficient of resistivity （α） was calculated from the ρ-Tcurve. The enthalpy （AH） and the specific heat （Cp） values were determined by differential scanning calorimetry analysis. In addition, the thermal conductivities of samples, obtained using the Wiedemann-Franz and Smith-Palmer equations, were compared with the experimental results. The results revealed that, the thermal conductivity values obtained using the Wiedemarm-Franz and Smith-Palmer equations for the Bi-2.0Zn-0.2Al （wt%） alloy are in the range of 5.2-6.5 W/Km and 15.2-16.4 W/Km, respectively.     

稀土三元配合物抗菌剂的合成及抗菌性研究

采用液相沉淀法合成了稀土席夫碱8-羟基喹啉配合物,通过核磁共振、红外光谱分析了其结构。通过抗菌实验对所制备的稀土新型三元配合物的抑菌效果进行了研究,结果表明,配合物对大肠杆菌、枯草杆菌和青霉菌均表现出不同程度的抑菌效果,其中对枯草杆菌具有中等的抑菌效果,对大肠杆菌具有强抑菌效果,而对青霉菌的抑菌效果最好。Gd配合物、Tb配合物和Yb配合物的抑菌效果明显好于La配合物和Nd配合物,这说明中、重稀土配合物的抑菌性能好于轻稀土配合物。在室温条件下,5种稀土三元配合物对3种细菌的抑制作用,均可达一周时间以上,说明所合成的稀土三元配合物抑菌效果稳定。