含二苯并-18-冠-6席夫碱型液晶冠醚钾配合物的合成与表征

以顺(反)-4,4＇-双[4-(4＇-正烷氧基联苯基-4-羧基) 苯亚氨基] 二苯并-18-冠-6（I和II）为配体合成了2个系列席夫碱型液晶冠醚钾配合物,产率分别为85.5%~92.1%和88.7%~90.7%。配合物的结构通过元素分析、IR、UV-Vis和AAS等方法确证。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明,所有配合物均具有热致液晶性,且随分子末端烷氧基碳原子数增加,其熔点和清亮点呈规律性变化。近晶相温度范围渐增,向列相温度范围递减。与配体相比,配合物液晶态温度范围变宽     

矩阵逆半群

讨论矩阵逆半群的一些基本性质, 证明矩阵逆半群的幂等元集是有限布尔格的子半格, 从而证明等秩矩阵逆半群是群, 然后完全确定二级矩阵逆半群的结构：一个二级矩阵逆半群或者同构于二级线性群,或者同构于二级线性群添加一个零元素,或者是交换线性群的有限半格, 或者满足其他一些性质; 对于由某些二级矩阵构成的集合, 我们给出了它们成为矩阵逆半群的充分必要条件.     

有序介孔有机金属 Pd(II) 的制备及其催化水介质中的 Suzuki 反应

 以有机金属 Pd 硅烷和乙基桥联硅烷为混合硅源, 在表面活性剂作用下进行共缩聚反应, 制备了有序介孔有机金属 Pd(II) 催化剂 Pd(II)-PMO(Et). 采用傅里叶变换红外光谱、核磁共振谱、X 射线衍射、透射电子显微镜和 N2 吸附脱附等手段对催化剂进行了表征. 结果表明, 与后嫁接法相比, 共聚法制得的催化剂活性位分散均匀, 孔道不易堵塞, 同时乙基修饰的孔壁增强了催化剂表面疏水性, 有利于反应物在孔道内的扩散和吸附. 在水介质 Suzuki 反应中, Pd(II)-PMO(Et) 的催化活性与均相催化剂 Pd(PPh3)2Cl2 的相当, 且可重复使用.     

铁和锰的化学状态对 LaFexMnyAl12-x-yO19 催化剂上 N2O 分解的影响

 以共沉淀法制备了 LaFexMnyAl12-x-yO19 六铝酸盐催化剂, 并用 X 射线衍射、扫描电镜、N2 吸附-脱附、紫外-可见漫反射光谱和穆斯堡尔谱对催化剂进行了表征, 考察了催化剂上高浓度 N2O 分解反应的性能. 结果表明, 在所考察的条件下, Mn 比 Fe 更有利于促进六铝酸盐晶相的形成. LaFexAl12-xO19 (x = 0.5, 1) 中 Fe 以 Fe3+位于六铝酸盐尖晶石结构中的四面体位和镜面层结构中的三角双锥位, 其中后者为 N2O 分解的主要活性中心. LaMnyAl12-yO19 (y = 0.5, 1) 中 Mn 优先以 Mn2+进入四面体位, 然后以 Mn3+进入尖晶石结构中的八面体位, 并成为 N2O 分解的主要活性中心.     

调控介孔硅分子筛的孔壁结构以提高吸附亚硝胺的效率

 针对高空速下捕获痕量毒物分子的环境净化要求, 尝试调控介孔材料孔壁结构以提高其吸附小分子环境污染物的效率. 通过调节合成体系的 pH 值、加入无机盐以及控制表面活性剂浓度等方法, 改变硅物种与模板剂胶束的组装速度或无机-有机液晶相的存在形态, 研制含有孔壁缺陷位的介孔分子筛新材料. 通过 X 射线衍射和低温氮气吸附研究了样品的结构特性, 并采用高分辨透射电镜和固体核磁技术证实了介孔材料孔壁缺陷位的形成. 以挥发性吡咯烷亚硝胺为靶标分子, 考察了所得材料的吸附性能. 结果表明, 大量缺陷空位的存在成倍地提高了介孔分子筛吸附挥发性亚硝胺的效率, 为设计研制环保新材料提供了新思路.     

稀土席夫碱配合物催化己内酯可控开环聚合

 通过稀土氯化物与席夫碱钠盐的交换反应制备了一系列以 3,5-二叔丁基水杨醛缩苯胺为配体的稀土席夫碱配合物. 对其中的钕席夫碱配合物进行了 X射线单晶衍射分析, 发现其单晶结构为五角双锥构型, 所得席夫碱稀土配合物可以单组分催化 ?-己内酯开环聚合. 深入研究了钕席夫碱配合物催化己内酯的开环聚合机理, 考察了不同聚合条件对单体转化率、产物分子量及分子量分布的影响. 结果表明, 该聚合反应速率为一级, 聚合反应具有较好的可控性. 聚合物端基分析表明, 聚合反应以配位-插入机理进行.     

[(NHC)CrCl(μ-Cl)(THF)]_2 and(NHC)_2CrCl_2(NHC=1,3-Diisopropyl-4,5-dimethylimidazole-2-ylidene):Syntheses,Structures,and Polymerization Activities

The preparation of divalent chromium N-heterocyclic carbene(NHC,1,3-diisopropyl4,5-dimethylimidazole-2-ylidene) compounds is reported.The reaction of 1:1 molar ratio of NHC with CrCl2 led to an isolation of [(NHC)CrCl(μ-Cl)(THF)]2(1),while that of 2:1 ratio resulted in the formation of(NHC)2CrCl2(2).1 can be considered as an intermediate in the formation of 2 and further converted into 2 by the addition of another equiv.of NHC.The reaction of 2 with CpNa afforded an ion pair compound [(NHC)2CrCp]+[Cp]-(3),indicating a strong coordination ability of NHC supplanting one of the ionic Cr-Cp bonding.In combination of methylalumoxane(MAO) as cocatalyst 1 and 2 both are active for catalyzing ethylene polymerization.     

Synthesis, Crystal Structure and Biological Activity of a Planar Copper Complex Derived from S-benzyldithiocarbazate

A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101(11),b = 16.952(3),c = 13.962(3) ,β = 92.458(4)°,V = 1586.7(5) 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F(000) = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ 2σ(Ⅰ) and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines (MKN45 and HepG2) by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.     

Photocatalytic Activities for Water Splitting of RuO_2-loaded MGa_2O_4（M=Zn,Ni） with d~（10） Configuration

MGa2O4(M=Zn,Ni) rods with similar crystallinity and BET surface area were prepared via a facile template-engaged reaction.The photocatalytic activities for water splitting of RuO2-loaded MGa2O4(M=Zn,Ni) were investigated under high-pressure Hg lamp.RuO2-loaded ZnGa2O4 catalyst exhibited much higher photocatalytic activity than RuO2-loaded NiGa2O4.Factors affecting the photocatalytic activities of RuO2-loaded MGa2O4(M=Zn,Ni) were discussed.It was suggested that the electronic structure of oxide semiconductor was a predominant factor of the photocatalytic behavior for RuO2-loaded MGa2O4(M=Zn,Ni).     

Synthesis and Crystal Structure of 2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ)

2,4-Diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol-copper(Ⅱ) has been designed and synthesized.The structure was determined by UV,IR and single-crystal X-ray study.The title complex crystallizes in the triclinic system,space group P1 with a=6.6090(13),b=10.377(2),c=12.550(3),α=113.29(3),β=93.84(3),γ=98.31(3)°,V=774.9(3)3,Dc=2.215g/cm3,C26H30CuO4N4I4,Mr=1033.68,F(000)=487,μ=4.726 mm-1,Z=1,the final R=0.0563 and wR=0.1475 for 2101 observed reflections(I2σ(I)).The central copper(Ⅱ) is four-coordinated by two nitrogen atoms and two oxygen atoms from two 3,5-diiodosalicylaldehyde-2-morpholinoethylamine Schiff bases.The complex is linked into a column by π-π stacking interaction.The complex was assayed for antibacterial activities against three Gram positive bacterial strains(B.subtilis,S.aureus and S.faecalis) and three Gram negative bacterial strains(E.coli,P.aeruginosa and E.cloacae) by MTT method.Fortunately,the title complex shows potent antibacterial activity against these six bacterial strains.