Synthesis and Crystal Structures of Four Novel Mo(W)/Cu/S Polymers Containing Thiolato Bridging Ligands

Four novel M/Cu/S polymers [Et₄N][MS₄Cu₃(S₂COEt)₂] (1a: M=Mo; 1b: M=W) and Et₄N][MS₄Cu₂SEt] (2a: M=Mo; 2b: M=W) have been prepared by reactions of [Et₄N]₂[MS₄] with CuS₂COEt and CuSEt. X-ray crystal structure determinations reveal that the polymeric anions of complexes 1a and 1b both consist of MS₄Cu₃ building blocks linked via bidentate [S₂COEt]⁻ bridging ligands to form 1D polymeric chains. The anion structures of the polymeric compounds 2a and 2b contain MS₄Cu₂ repeating units which are connected via μ-SEt⁻ ligands forming a zigzag chain running down the crystallographic b axis.     

铁体系催化剂制备方式对催化活性影响的研究

通过Ｔｙｎｄａｌ效应，电镜观察，电导率测定，结合聚合实验，发现铁体系催化剂在加氢汽油介质中为胶体催化剂，而且是聚结不稳定胶体体系．催化剂各组分配比，加入顺序影响胶粒的形态，因而影响到催化活性与聚合物微观结构．其中较佳配比，较佳加入顺序（Ｆｅ）∶（Ｃｌ）∶（Ａｌ）＝１∶２．５∶２０，催化剂颗粒比较小，均匀，因而比表面积大，催化活性高，相反其他配比的颗粒大，不均匀，催化活性低．陈化使胶粒聚集变大，故催化活性降低．     

Submicrosecond rearrangeable nonblocking silicon-on-insulator thermo-optic 4x4 switch matrix

A rearrangeable nonblocking silicon-on-insulator-based thermo-optic 4x4 switch matrix is designed and fabricated. A spot-size converter is integrated to reduce the insertion loss, and a new driving circuit is designed to improve the response speed. The insertion loss is less than 10 dB, and the response time is 950 ns.     

Time Jitters in Multiple-Core Fiber of Ring Structure

Property of soliton propagation is analyzed by using self-companying operator method in multiple-core fiber of ring structure. The results show that the time jitters of soliton transmission in every core relate to the relative amplitude among the input solitons in the multiple-core fiber.     

Synthesis and X-ray structure studies of complex [Cu(o-phenanthroline)2 (saccharin)] · (saccharin) · 2 H2O

The title compound has been synthesized and its crystal structure determined at room temperature, M_r = 824.34, triclinic, space group P–1(2), a = 13.622(4), b = 13.770(4), c = 11.167(3) Å; α = 104.83(2), β = 110.01(2), γ = 62.04(2) degree; U = 1727.0(9) ų, Z = 2, D_calc = 1.59 g/cm³. The final R is 0.066 for 3299 independent observed reflections with I ≧ 3σ(I). The crystal structure consists of repeated [Cu(o-phen)₂(sac)]⁺ cations, non-coordinated saccharin anion and two lattice water. And the central ion Cu²⁺ forms a trigonal-bipyramidal stereochemistry.     

1,2-聚丁二烯长链支化的研究

本文研究了1,2-结构含量在80～90%的1,2-聚丁二烯的长链支化,发现聚合物的立体规整性与聚合物的分子量无关,可以用GPC-自动粘度计联用技术研究其长链支化,产生支化的临界分子量为40万左右。     

烷基功能化聚烯丙基缩水甘油醚的制备及对PVC的增塑及抗静电作用

利用阴离子开环聚合(AROP)及巯基-烯点击反应相结合的路线构筑了一种新型烷基功能化聚醚, 考察了其对聚氯乙烯(PVC)的增塑及抗静电作用. 首先, 以烯丙基缩水甘油醚为单体, 利用AROP制备聚烯丙基缩水甘油醚(PAGE)中间产物; 然后, 以PAGE为前驱体, 借助巯基-烯点击反应将柔性烷基引入其侧链, 获得烷基功能化聚烯丙基缩水甘油醚(PAGE_butane)目标产物. 核磁共振波谱(NMR)及凝胶渗透色谱(GPC)结果表明, 所得聚合物结构与设计一致, 且PAGE的分子量可通过改变单体与引发剂的投料比灵活调控. 热性能研究结果显示柔性烷基的键入导致PAGE的玻璃化转变温度(T_g)进一步降低. PAGE_butane的T_g为-74.97 ℃, 且具有较好的热稳定性. PAGE_butane在不损失PVC强度的同时可明显提升其韧性, 同时可有效降低其表面电阻率, 产生一定的抗静电效果. 与邻苯二甲酸二(2-乙基)己酯(DOP)增塑剂相比, PAGE_butane体现出更优异的耐抽出及耐挥发性.     

Determination of the Activity Coefficients of NaCl in the System NaCl–NH4Cl–H2O

Using ion-selective electrode(s) (ISE) the activity coefficients of NaCl in the system NaCl–NH₄Cl–H₂O at 10, 25, and 40°C were measured by a computer-controlled automatic titration system. The ionic strength fractions of NH₄Cl were 0.2, 0.4, 0.6, and 0.8, respectively. It was found that the influence of the NH₄⁺ cation on the Na glass ISE was small enough to be neglected up to 3.0 mol-kg^-1. The Pitzer equation was adopted to calculate the activity coefficients of NaCl in this system and compared with the experimental data. Comparison of results indicates that the Pitzer parameters correlated from solubility data are suitable for calculating the activity coefficients for this system within the saturated solutions.     

Syntheses,structures and catalytic activities of low-coordinated rare-earth metal complexes containing 2,2′-pyridylpyrrolides

Reactions of the ligand precursors 2-(2′-pyridyl)-3,5-Me₂-pyrrole ( L ¹ H) and 2-(2-pyridyl)-3,4,5-Me₃-pyrrole ( L ² H) with [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ in toluene afforded a series of low-coordinated rare-earth metal bis-amido complexes L ¹ RE[N(SiMe₃)₂]₂ [RE = Y ( 1a ), Dy ( 1b ), Er ( 1c ), Yb ( 1d )] and L ² RE[N(SiMe₃)₂]₂ [RE = Y ( 2a ), Dy ( 2b ), Er ( 2c ), Yb ( 2d )]. With the ionic radius of rare-earth metal increasing, the reaction of L ¹ H and [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ gave dinuclear complexes ( L ¹ )₂RE(μ-Cl)(μ-η⁵:η¹:η¹- L ¹ )RE( L ¹ )[N(SiMe₃)₂]₂ [RE = Sm ( 1e ), Pr ( 1f )]; however, the reaction of L ² H and [(Me₃Si)₂N]₃Sm(μ-Cl)Li(THF)₃ afforded ( L ² )₂Sm[N(SiMe₃)₂]₂ ( 2e ). Results indicated that the ionic radius of rare-earth metal and subtle change in the ligands have substantial effects on the structure and bonding mode of complexes. The complexes showed a high catalytic activity for the ring-opening reaction of cyclohexene oxide with amines to afford various β-aminoalcohols under mild solvent-free conditions.