腙类配合物的研究——Ⅱ.二茂铁芳酰基腙和它们的一些过渡金属螯合物

通过甲酰基二茂铁与相应芳酰基肼的缩合反应合成了二茂铁基的苯甲酰基、对-甲氧基苯甲酰基和间-硝基苯甲酰基腙,并制备了它们与Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Mn(Ⅱ)醋酸盐的十种整合物。元素分析、IR和PMR谱的测定结果表明,这些金属有机配体是以烯醇式进行配位的。     

Chemical Constituents of Ailanthus triphysa

Two new compounds,8(14),15-isopimaradiene-2α，３α，19-triol(1),and 6α，７β－dihydroxy-17(20)-cis-5α－pregna-16-one(2),together with four known copounds,a oxygenated rare phyllocladane,phyllocladan-16α，19-diol(3),kaempferol-3-0-β－Ｄ-galactopyranosied,kaempferol-3-0-α－Ｌ－rhamnopyranoside and scopoletin, were isolated from the leaves of Ailanthus tripysa.Structures of 1-3 were elucidated on the basis of spectroscopic data as compared with related compounds.     

HCF(~1A'''')+SO_2反应的动力学研究

用激光光解-激光诱导荧光方法研究了室温下(T=293K)HCF(X%A′)自由基与SO2分子的反应动力学.实验中1HCF(X%A′)自由基是由213nm激光光解HCFBr2产生的,用激光诱导荧光(LIF)检测HCF(X%A′)自由基的相对浓度随着11反应时间的变化,得到此反应的二级反应速率常数为:k=(1.81±0.15)×10-12cm3?molecule-1?s-1,体系总压为1862Pa.高精度理论计算表明,HCF(X%A′)和SO2分子反应的机理是典型的加成-消除反应.我们运用RRKM-TST理论计算了1此二级反应速率常数的温度效应和压力效应,计算结果和室温下测定的二级反应速率常数符合得较好.     

原子簇P12（D3d）的理论研究

利用Ｇａｕｓｓｉａｎ－９２程序在６－３１Ｇ基组下优化Ｐ１２（Ｄ３ｄ）构型，研究了３Ｐ４（Ｔｄ）→Ｐ１２（Ｄ３ｄ）的相对能量，计算结果为△Ｅ＝Ｅｐ１２（Ｄ３ｄ）－３Ｅｐ４（Ｔｄ）＝－７９．８４４ｋＪ／ｍｏｌ，优化Ｐ１２（Ｄ３ｄ）获得的Ｐ－Ｐ键键长接近于实验测得的Ｐ－Ｐ单键键长，并进一步在该基组下计算了Ｐ１２（Ｄ３ｄ）原子簇的振动频率，得到的全部为正频率，表明原子簇Ｐ１２的Ｄ３ｄ构型是位能面上的稳定点     

New Photoluminescence Phenomena of Ge／SiO2 Glass Synthesized by Sol-gel Method

New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV) and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photoluminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS).     

Linking cyano-bridged ladders by azide to form a layered metamagnet

Cyano-bridged corrugated ladder-like chains are connected by mu(1,1)-N(3) (end-on, EO) bridges to form a layered coordination polymer, [Mn(N(3))(CH(3)OH)[Cr(phen)(CN)(4)].CH(3)OH (2), which is the first mixed cyano-azide bridged compound, and shows metamagnetism below 21.8 K, a temperature much higher than that (3.4 K) of the crossed double chain [Cr(phen)(CN)(4)](2) [Mn(H(2)O)(2)].4H(2)O (1) based on the same building block [Cr(phen)(CN)(4)](-).     

A New Technique of Synthesizing 10—Hydroxy—5—methyl—5,10—dihydrophenophosphazine 10—Oxide

10-Hydroxy-5-methyl-5,10-dihydrophenophosphazine 10-oxide(1)was prepared by a new technique of treating 10-methoxy-5,10-dihydrophenophosphazine 10-oxide(2)with an equivalent of NaH in anhydrous DMF,and then at 120℃ for 3-4h,which not only avoided poisonous and expensive methyl iodide used in literature,but made the consumption of NaH greatly decrease as well.The possible reaction mechanism was also described.The chemical structure of 1 was confiremed by IR,NMR,and mass spectroscopy.     

Structure and Two-photon Excited Blue Fluorescence of an Asymmetrical Substituted Stilbene

In common fluorescence process, molecular excitation is caused by the absorption of at least a single photon with shorter wavelength. When certain laser is used as the pump source, some compounds can be excited by simultaneous absorption of at least two photons and then the emission of up-converted fluorescence may occur. This process is called two-photon excited fluorescence (TPEF)1,2. Because of several advantages of TPEF, including intrinsic high three-dimensional resolution and the p…     

TS和PTS单晶体的热刺激电流

测定了双(对甲基磺酸)2,4-己二炔-1,6-二醇酯(TS)及其不同聚合程度TS-PTS混合体和完全聚合的聚合物PTS在100-300K温度范围内的热刺激电流。在沿分子堆砌方向上(对PTS则是大分子链方向)上观察到了它们的热刺激电流,并在相应于它们相变152K和192K处呈现热刺激电流峰。研究了聚合程度对相变的影响,绘制了TS-PTS体系的相图。对另三个热刺激电流峰的归属作了定性解释。     

催化剂三氟化硼乙醚在环醚类阳离子聚合中的一个性质

本文以三氟化硼乙醚作催化剂,在一缩二乙二醇存在下,进行了1,1,5-三氢八氟戊基缩水甘油醚与四氢呋喃的共聚合反应,用气相色谱、薄层色谱、红外光谱和核磁共振等方法研究了从共聚物中分离出来的物质,发现含有带乙氧基的小分子化合物,它是由催化剂带入到聚合体系中的轻微量乙醚的作用而产生的,同时还会产生带乙氧基的单羟基共聚物,以三氟化硼四氢呋喃代替三氟化硼乙醚进行了同样的共聚合反应,所得的共聚物中单羟基共聚物较少。