Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

Effects of Polymer Bridging and Electrostatics on the Rheological Behavior of Aqueous Colloidal Dispersions†

Effects of a low molecular weight physically adsorbed polyethylene oxide (PEO) and the range of the electrostatic repulsion on the rheological behavior of silica dispersions (as a model system) has been investigated. Particular attention is given to the evolution of the rheological behavior with increasing the polymer concentration in the system and also effectiveness of the polymer as a dispersant under extreme conditions (high ionic strength). Results indicate that at small separation distances and low polymer coverage, the polymer chains are long enough to adsorb on the surface of two particles simultaneously causing bridging flocculation in the system and hence increasing the viscosity and linear viscoelastic functions of the dispersion. A significant increase was observed in the viscosity of the dispersion at salt concentrations high enough to eliminate electrostatics between the particles. Under these conditions,the viscosity of the system increased significantly when PEO was added to the dispersion showing that at high electrolyte concentrations, a neutral polymer such as PEO is not able to stabilize the system.     

硅酸盐中桥联键的机制及其性质的CNDO/2法研究

法计算模型,分析了桥联键的成键机制,解释了硅酸盐的通常性质。以体系总能量随桥角变化关系,解释了硅酸盐矿物及沸石分子筛中桥角Si-O-T出现的范围和几率。 由计算结果还发现,桥氧上具有较高的非键p-电子电荷Q_o~n,并随桥氧的第三配原子性质和距离R(M-O~(br))而变化,使桥氧具有授受电子的双重性质。在此基础上,探讨了沸石分子筛的碳离子催化活性机理,提出了锁与匙匹配原子对的催化活性中心的新观点。     

两性田菁胶在处理生活污水中的助凝作用

研究了以聚合硫酸铁为主凝剂、两性田菁胶(ASG)为助凝剂处理城市生活废水的各种影响因素.实验结果表明:聚合硫酸铁和两性田菁胶分别以200mg/L和10mg/L的复配浓度、pH值接近7时混凝效果最佳,CODCr去除率达到近80%,处理后废水CODCr达到国家排放标准.     

Early-stage flocculation kinetics of polystyrene latex particles with polyelectrolytes studied in the standardized mixing: Contrast of excess and moderate polyelectrolyte dosage

Standardized mixing procedure was applied to the analysis of flocculation of polystyrene latex (PSL) particles with polyelectrolytes. After confirming the initial enhancement of flocculation rate in the very beginning followed by abrupt stop with excess dosage, attention was shifted to the system of moderate dosage. In the former, effects of ionic strength were further analyzed to find the consistency with adsorption isotherm. In the latter, flocculation started slowly in the beginning, sometime slower than salt-induced rapid coagulation, however, the rate gradually increases in the middle stage. Often, the increased rate exceeds that of salt-induced rapid coagulation. This behavior emerged more clearly in the case of lower ionic strength. This is the indication that the rate of relaxation of polymer on the colloidal surface is a function of surface coverage and ionic strength. The ultimate degree of flocculation is usually higher than that observed for excess dosage. The size distribution of flocs was also examined, however, no clear difference between different experimental conditions was confirmed for the same degree of flocculation.     

Coupling between polymer adsorption and colloidal particle aggregation

Studies of the adsorption of high molecular weight polymers on colloidal latex and silica particles and their subsequent flocculation were carried out. Neutral polyethylene oxide samples with both a narrow and a broad molecular weight distribution were used together with low charged cationic copolymers. The influence of the particle concentration and polymer dose on the flocculation were systematically investigated under quiescent conditions.Equilibrium bridging only occurred with polyelectrolyte, even in very dilute suspensions, at high particle coverage. In contrast to this, non-equilibrium bridging occurred with both neutral polymer and polyelectrolytes but only for more concentrated suspensions and small amounts of adsorbed polymer. Polymer adsorption in dilute suspensions, which did not show particle aggregation was measured an electrophoretic technique. In more concentrated suspensions, where flocculation takes place, we found that aggregation prevents further polymer adsorption and induces both an excluded volume and a surface effect. The consequences on the shape of the isotherms differ according to the aggregation mechanism.A significant decrease of the amount, , of adsorbed polymer is observed with non-equilibrium bridging. When both mechanisms simultaneously contribute to the aggregation, the value of depends on their relative importance. In the intermediate range of copolymer dose their respective contributions are critically sensitive to the details of the mixing step and stirring, leading to non reproducible experimental results.     

配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

配位聚合物{[MnL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成及其磁学性质

合成和表征了一种新的Schiff碱配合物MnL(ClO4)*3H2O(1)(其中L为n(水杨醛)∶n(二乙撑三胺)=1∶1缩合而成的Schiff碱).1与FeSO4*7H2O和K3[Fe(ox)3]*3H2O(ox=oxalate)进一步反应,生成了双金属层状配位聚合物{[MnL][FeⅡFeⅢ(ox)3]*1.5H2O}∞(2).IR和Mssbauer谱测定结果表明,2具有二维层状结构,其阴离子层由[FeⅡFeⅢ(ox)3]-单元构成.变温磁化率(5K～100K)测试结果表明,2中的自旋载体之间存在反铁磁交换作用.5K时的磁滞现象表明2在低温时可能存在铁磁有序,这可能是亚铁磁或自旋倾斜造成的.     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).