Ln[CrMo6O24H6]杂多配合物的合成与表征

合成了具有Anderson结构的Ln[CrMo6O24H6]（Ln^3 =La,Ce,Pr,Nd,Sm,Gd,Dy,Yb）的8种杂多配合物，此类配合物属Anderson结构B型，通过ICP和TG及元素组成分析，确定了配合物的组成，利用IR，UV，^95Mo-NMR,ESR,XRD等方法进行了表征，借助TG－DTA、不同温度下的IR和XRD以及水溶性实验研究了配合物热解性质，结果表明，配合物分解温度为350℃-400℃。     

Anderson型杂多酸-DABCO复合二维相变晶体材料的合成及介电性质

以1.4-二氮杂二环[2.2.2]辛烷(DABCO)氟硼酸盐与(NH4)3[FeMo6 O24 H6]·7H2 O多酸盐为原料,通过H管水溶液界面扩散方式合成一种新颖的Anderson型超分子化合物(H2 DABCO)2[FeMo6 O24 H4]·4H2 O(1).并通过红外光谱、单晶X衍射、元素分析、XRD粉末衍射...     

硒钼杂多配合物及其稀土盐的合成及催化苯酚羟化反应的研究

合成了杂多配合物(NH4)6[Se2Mo8O31]·5H2O,在此基础上合成了其稀土盐Ln2[Se2Mo8O31]·xH2O(Ln=La3+,Ce3+,Nd3+,Sm3+),探讨了这些杂多配合物在苯酚羟化反应中的催化作用,发现稀土盐的催化效果低于配合物(NH4)6[Se2Mo8O31]·5H2O的催化效果;在溶剂丙酮中苯酚的转化率大于在乙腈中的转化率。通过正交法研究了反应温度、原料比、反应时间和催化剂用量对苯酚转化率、产品分布和过氧化有效转化率的影响,找到了最佳反应条件,即在苯酚/H2O2(摩尔比)为1,催化剂用量10g·mol-1,反应温度70℃,反应时间4h时,得到苯酚转化率29.65%,产品选择率77.2%。     

第二结构导向剂诱导形成的二维有机模板稀土硫酸盐（英文）

水热条件下合成了具有超大孔道和层状结构的有机模板稀土硫酸盐。超大孔道的稀土硫酸盐(1)的分子式为[(CH3)2NH2]9[Pr5(SO4)12]·2H2O,它展现出有趣的交叉二十元环孔道结构。层状的稀土硫酸盐的分子式为[H3O]3[(CH3)2NH2]3[Ln2(SO4)6](Ln=Pr,2;Nd,3),它可以被看作是由双链和八元环结合而成。这3种化合物的合成揭示了大的有机胺(三聚氰胺)可能用作为第二结构导向剂,阻止形成高维数的无机骨架,从而诱导了二维层状结构稀土硫酸盐晶体的生长。对化合物1和3的磁性进行了研究,测试的温度范围在2~300 K。     

甘氨酸的杂多酸超分子化合物的合成及性质研究

首次合成了甘氨酸的Keggin结构杂多酸超分子化合物(HGly)3[PW12O40]·5H2O(HGly)4[SiW12O40]·4H2O,用元素分析,IR,UV,TG-DTA,XRD和NMR等方法对标题化合物进行了表征,并讨论了它们的合成条件及结构特性.     

基于柔性硫代二乙酸配体的镧系配位聚合物的合成、结构和荧光性质

利用硫代二乙酸配体[thiodiacetic acid = H2tda]与稀土盐[SmCl3·nH2O,DyCl3·nH2O]反应合成了两种新型稀土配合物[Ln2(tda)3(H2O)2]n (Ln = Sm(1), Dy(2)),单晶结构分析表明：两个配合物结构相同,均是通过以共边多面体[Ln2O16]为基本单元的一维稀土金属链拓展而成的二维层状结构。有趣的是,在配合物中,硫代二乙酸配体展现了两种配位模式：双“顺-顺桥式双齿、螫合-桥式三齿”模式和双“螯合-桥式三齿、顺-反桥式双齿”模式;正是通过配体这两种配位方式的连接,上述一维稀土金属链扩展为具有(3,4,5,6)连接(47·68)(44·66) (45·6)(46)(43)拓扑结构的二维网络。荧光性质研究表明,在室温下镝配合物呈现黄色荧光,钐配合物呈现鲑鱼粉色荧光。     

13-钒镍(锰)杂多酸稀土盐的合成及其镨盐抗肿瘤活性的研究 Ⅰ.

本文以离子交换-复分解法合成了未见文献报道的13-钒镍(锰)杂多酸的稀土盐。通式为Ln2H[MV13O38].nH2O[Ln=La, Ce, Pr, Nd, Sm, Eu; M=Ni, Mn]。经元素分析、红外光谱、电子顺磁共振、磁化率及^5^1V NMR核磁共振谱对其结构进行了表征。微量细胞培养四氮唑(MTT)法实验表明: 13-钒镍(锰)杂多阴离子的镨盐对多种人癌细胞具有较强的杀伤作用, 显示出较强的体外抗肿瘤活性。     

水杨醛缩氨基硫脲稀土有机配合物的合成及表征

由水杨醛缩氨基硫脲与三茂稀土Cp3Ln(Ln=La，Tb，Dy，Ho，Er，Yb)在THF中反应合成了6种新型配合物,经元素分析、IR，MR，XPS等表征表明它们为同时含Ln-0，Ln-N和Ln-S键的二聚体[CpLn(μ-O)C3H7N3S]2。     

原位[2+3]环合成法制备四唑化合物、结构及荧光性质(英文)

利用氰基吡啶(4-氰基吡啶和3-氰基吡啶)与稀土硝酸盐作用(Ln=Nd,Eu,Yb),通过原位[2+3]环加成反应合成得到了4个稀土四唑离子型化合物,Ln(H2O)8·3(p-TPD)·2(p-HTPD)·7H2O),(Ln=Nd(1),Eu(2),Yb(3)),p-TPD=4-tetrazoylpyridine,p-HTPD=protonated 4-tetrazoylpyridine)以及Ln(H2O)8·3(m-TPD)·6H2O(m-TPD=3-tetrazoylpyridine,Ln=Yb(4))。X-射线单晶结构分析显示,在配合物1~4中,稀土金属离子与配体分别处于不同的两层,[Ln(H2O)8]3+结构单元与p-TPD以及水分子通过氢键作用形成阳离子层(A层),同时p-TPD与p-HTPD通过π-π堆积与氢键作用形成阴离子层(B层)。固态荧光分析表明,配合物1,2,4在405、400、494 nm处出现了最大强度的发射峰值;而配合物3在618、592及462 nm出现了最大强度的发射峰值。热重分析表明配合物1~4在70~120℃范围内有1个失重,而在180~220℃范围内配合物开始分解。     

聚合物裂解法制备稀土铁氧体LnFeO_3(Ln=Pr,Sm,Eu,Gd)纳米晶

以丙烯酸和稀土离子为原料,经原位聚合裂解法合成聚合物前驱体[1Ln(Ln=Pr,Sm,Eu,Gd)];1Ln在空气氛中于500℃热解3 h制得4个稀土铁氧体纳米晶[Ln Fe O3(2Pr~2Gd)],其结构和形貌经FT-IR,TGA,XRD和SEM确证。     

6, 6-Dialkyl- und 6, 6-Polymethylen-fulvene

The electronic, infrared and NMR spectra of 6, 6-dialkyl-fulvenes and of 6, 6-poly-methylene-fulvenes are reported.     

6A6B, 6A6C,and 6A6D-ditosylates of β-cyclodextrin

Regio-isomers, 6A6B, 6A6C, and 6A6D-ditosylates of β-cyclodextrin prepared by the reaction of β-cyclodextrin with tosyl chloride were easily and effectively separated through reversed phase column chromatography and assigned.     

Preparation of 6-chloro-6-desoxy- and 6-iodo-6-desoxycellulose

Conclusions The reaction of 2,3-di-O-acetylcellulose with N-chloro- or N-iodosuccinimide and triphenylphosphine gave the 6-chloro-6-desoxy- and 6-iodo-6-desoxycellulose acetates with a respective degree of substitution (DS) in halogen of 0.8–1.0 and 0.7. The deacetylation of these compounds gave 6-chloro-6-desoxycellulose (DS 0.8) and 6-iodo-6-desoxycellulose (DS 0.6).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2158–2160, September, 1977.     

Isomer stability of N6C6H6 cages

Recent theoretical studies have identified carbon-nitrogen cages that are potentially stable high energy density materials (HEDM). One such molecule is an N(6)C(6)H(6) cage in which a six-membered ring of nitrogen is bonded to C(3)H(3) triangles on both sides. This molecule is based on the structure of the most stable N(12) cage, with six carbon atoms substituted into the structure. In the current study, several N(6)C(6)H(6) isomers (including the previously studied cage) are examined by theoretical calculations to determine which is actually the most stable. Stability will be evaluated from two points of view: (1) thermodynamic stability of one isomer versus another and (2) kinetic stability of each isomer as determined by the energetics of bond breaking. Density functional theory (B3LYP), perturbation theory (MP2 and MP4), and coupled-cluster theory (CCSD(T)) are used in this study, along with the correlation-consistent basis sets of Dunning. Trends in thermodynamic and kinetic stability are discussed.     

Regioselective synthesis of 6-amino- and 6-amido-6-deoxypullulans

Hydrophobically modified polysaccharides that contain amine and amide groups possess valuable features for drug delivery and other applications. These chemical groups are known to play a fundamental role in the biological activity of important polysaccharides. Pullulan is known for its non-toxicity and biocompatibility, therefore, we have applied the versatile Staudinger reaction for the synthesis of regioselectively substituted pullulan derivatives containing amine or amide groups with promise for biomedical applications. The synthesis began with the regioselective bromination of pullulan at C-6 with N-bromosuccinimide and triphenylphosphine, providing 6-bromo-6-deoxy-pullulan, which is soluble in a range of organic solvents and therefore is a dynamic intermediate for the synthesis of other pullulan derivatives. Azide displacement of bromide from 6-bromo-6-deoxy-pullulan esters yielded the corresponding 6-azido-6-deoxy-pullulan esters. Staudinger reduction of these azides efficiently and chemoselectively afforded the corresponding amino- or amidopullulans.