锡苯和铅苯二聚反应的理论研究

采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯.     

插烯规则及其应用

介绍了插烯规则的提出及其在解释和预测“异常”反应和“异常”产物以及“异常”理化性质上的应用     

[Na(18-C-6)]2[Cu(i-mnt)2]的合成与结构分析

研究了18-冠-6与Na2[Cu(i-mnt)2][i-mnt=异丁二腈烯二硫醇阴离子,S2CC(CN)2-2]的反应,得到的配合物[Na(18-C-6)]2[Cu(i-mnt)2](1)通过元素分析、红外光谱、X射线单晶衍射进行了结构分析.配合物为单斜晶系,空间群P2(1)/c.晶体学结构数据a=1.2819(11),b=1.1793(10),c=1.4928(13)nm,β=99.121(16)°,V=2.228(3)nm3,Z=2,Dcaled.=1.369g/cm3,F(000)=958,R1=0.0521,wR2=0.1003.1中的[Cu(i-mnt)2]基团通过配体i-mnt的氮原子与两个[Na(18-C-6)]基团中的钠原子成键,形成稳定的中性配合物.     

Structural Characteristics of Liquid Sn

We investigate the structural properties of liquid Sn. With the help of the internal friction (tanФ) method, it is found that a peak appears in the tan Ф - T curve, suggesting that an anomalous discontinuous temperatureinduced structure change may take place in liquid Sn. From the experimental data of pair distribution functions, we calculate the viscosity η and the excess entropy S and it is found that there are a peak of viscosity in the η-T curve and a bend of excess entropy in the S - T curve, which give a positive support to the appearance of the internal-friction peak in the tan Ф- T curve.     

钌(Ⅱ)卟啉催化顺式二苯乙烯类化合物的选择性合成

由芳醛制得的腙盐在钌(Ⅱ)卟啉催化下发生自身偶合，以较高收率合成了二苯乙烯类化合物(～90％的顺式选择性)。部分中间体及目标化合物的结构经^1H NMR，^13C NMR和MS表征。     

Three Novel Eremophilanolides from Ligularia virgaurea spp. oligocephala

From the alcoholic extract of the whole plant of Ligularia virgaurea spp. oligocephala, three novel eremophilane sesquiterpene lactones, 6α, 10α-dihydroxy- 1-oxoeremophila-7(11), 8(9)-dien-8, 12-olide, 613, 10α-dihydroxy-1-oxoeremophila-7 (ll), 8 (9)-dien-8, 12-olide and 10α-hydroxy-1-oxoeremophila-7(l 1), 8(9)-dien-8, 12-olide were isolated. Their structures were elucidated by various spectroscopic methods including intensive 2D NMR techniques (COSY,HMQC, HMBC and ^1H-^1H NOESY) and HR-MS.     

Crystal Structures of Two Potential Tumor Imaging Agents and Therapeutic Agents Copper（Ⅱ） Ternary Complexes with Salicylidene-tyrosinato Schiff Base and Nitrogen-donor Chelating Lewis Base

The crystal structures of two potential tumor imaging agents and therapeutic agents -copper(Ⅱ) complexes with salicylidene-tyrosinato Schiff base and nitrogen-donor chelating Lewis base, [Cu(sal-tyr)(bipy)] 1 and [Cu(sal-tyr)(phen)]2CH3OH 2 are presented. Our work is helpful to get deep understanding of novel 64Cu tumor imaging agents and therapeutic agents.     

14β-甲磺酰氧基对映-贝壳杉二萜重排反应

本文研究了一类具有15-C与16-C单键的14β-甲磺酰氧基对映-贝壳杉烷(烯)(6,7和8)在Zn-EtOH体系中的重排反应, 它们均能重排成6, 7, 5, 5并环系统的化合物3, 12, 13a和13b。8重排时生成一个8-OEt化合物, 为这类化合物重排时经过阳离子中间体提供了一个证据。     

Sn-C60薄膜的紫外吸收光谱和X-射线衍射谱分析

对Sn-C60薄膜进行紫外可见光吸收，X-射线衍射和扫描电镜的测定结果显示，薄膜样品紫外可见光吸收的两个短波段吸收峰比纯C60薄膜的吸收峰显著下降，说明Sn-C60薄膜的电子光吸收跃迁为间接跃迁，能带中有杂质能级的存在；样品的X射线衍射峰则对应于面心立方结构；扫描电镜结果显示薄膜为纳米级颗粒组成。     

聚芳香杂环甲烯的三阶非线性光学效应与时间分辨光克尔效应

合成了一系列聚芳香杂环甲烯,包括聚吡咯甲烯和聚噻吩甲烯.采用四波混频法研究材料的共振三阶非线性光学效应(λ＝532nm),其共振二阶超分子极化率γ三阶非线性光学系数分别达到10^-30esu和10^-8esu.选择具有良好溶解性、成膜性的聚吡咯对二甲氨基苯甲烯(PPDMAB),采用飞秒时间分辨光克尔效应方法研究材料的非共振三阶非线性光学效应(λ=790nm).实验表明,翠绿亚胺碱溶液的光克尔信号仅表现一超快响应的成分,归功于π电子云扭转产生的非共振激发.PPDMAB的非共振二阶超分子极化率γ三阶非线性光学系数分别达到γ=5.78×10^-32esu和χ⁽³⁾=1.26×10^-10esu.