Copper(II) complexes of 2-aminoacetophenone N(4)-substituted thiosemicarbazones

Mononuclear copper(II) complexes with 2-aminoacetophenone thiosemicarbazone and three N(4)-substituted thiosemicarbazones have been prepared in ethanolic solution and characterized by physical and spectral methods. I.r., electronic and e.s.r. spectra of the complexes, as well as i.r., electronic, and ¹H- and ¹³C-n.m.r. spectra of the thiosemicarbazones, have been obtained. The 2-aminoacetophenone thiosemicarbazones coordinate as neutral ligands via the thiosemicarbazone moiety's azomethine nitrogen and thione sulfur, except for the piperidylthiosemicarbazone, which undergoes deprotonation and coordinates via the thiolato sulfur, as well as through the azomethine nitrogen. Complexes formed in the presence of triethylamine also form complexes with the anionic form of these thiosemicarbazones.     

The enthalpies of formation of bis-(benzene)molybdenum and of bis-(toluene)tungsten

Microcalorimetric measurements at 520–523 K of the heats of thermal decomposition and of iodination of bis-(benzene)molybdenum and of bis-(toluene)tungsten have led to the values (kJ mol^?): ΔH^o_f[Mo(η-C₆H₆)₂, c] = (235.3 ± 8) and ΔH^o_f[W(η⁶-C₇H₈)₂, c] = (242.2 ± 8) for the standard enthalpies of formation at 25°C. The corresponding ΔH^o_f(g) values, using available and estimated enthalpies of sublimation, are (329.9 ± 11) and 352.2 ± 11) respectively, from which the metalligand mean bond-dissociation enthalpies, $\text{D}$(Mo—benzene) = (247.0 ± 6) and $\text{D}$(W—toluene) = (304.0 ± 6) kJ mol^?1, are derived.     

Spectral and structural studies of cobalt(II,III), nickel(II), and copper(II) complexes of dehydroacetic acid N4-dialkyl- and 3-azacyclothiosemicarbazones

Co^II,III, Ni^II, and Cu^II complexes of new dehydroacetic acid N4-substituted thiosemicarbazones have been studied. The substituted thiosemicarbazones, N4-dimethyl-(DA4DM), N4-diethyl-(DA4DE), 3-piperidyl-(DApip) and 3-hexamethyleneiminyl-(DAhexim), when reacted with the metal chlorides, produced two Co^II complexes, [Co(DA4DE)Cl₂] and [Co(DAhexim)₂Cl₂]; two Co^III complexes, [Co(DA4DM-H)₂Cl] and [Co(DApip-H)(DApip-2H)]; a paramagnetic Ni^II complex, [Ni(DAhexim)(DAhexim-H)Cl]; three diamagnetic Ni^II complexes, [Ni(DA4DM-H)Cl], [Ni(DA4DE-H)Cl] and [Ni(DApip-H)Cl]; and four Cu^II complexes with the analogous stoichiometry of the latter three Ni^II complexes. These new thiosemicarbazones have been characterized by their melting points, as well as i.r., electronic and ¹H-n.m.r. spectra. The metal complexes have been characterized by i.r. and electronic spectra, and when possible, n.m.r. and e.s.r. spectra, as well as elemental analyses, molar conductivities, and magnetic susceptibilities. The crystal and molecular structure of the four-coordinate Cu^II complex, [Cu(DAhexim-H)Cl] has been determined by single crystal X-ray diffraction and the anionic ligand coordinates via an oxygen of the dehydroacetic acid and the thiosemicarbazone moiety's imine nitrogen and thione sulfur.     

Fabrication of Co/CoO Exchange Bias System by Ion Implantation and Its Magnetic Properties

We use ion implantation as a new approach to build an anti-ferromagnetic （AFM） cluster embedded exchange bias （EB） system. Co film with thickness of 130nm is deposited on the Si （111） substrate using magnetron sputtering, 60keV O＋ is chosen to implanted into the Co film to form CoO AFM clusters coupling with Co matrix at the interface. By measuring the hysteresis loop after field-cooling, significant shifts of loop along the applied field are confirmed. When increasing the implantation dose to 2×1017/cm2 and annealed samples in N2 atmosphere, we obtain the highest HEB to 458Oe.     

pH值对水热合成磷酸铋的光催化性能的影响

利用水热法通过调节溶液的pH值合成了不同物相和形貌的磷酸铋.用X射线衍射仪(XRD)和扫描电子显微镜(SEM)对样品进行了物相和形貌表征,并以10 mg·L-1的亚甲基蓝溶液为目标降解物,对材料的光催化降解性能进行了评价.结果表明:前驱物溶液的pH值对磷酸铋的形貌、物相和光催化性能都有较大影响.前驱物溶液pH值为1.3时制得的磷酸铋的光催化性能最高,室温汞灯照射20 min,亚甲基蓝的降解率可达到99.61;.     

利用卟啉中位羧基基团直接缩合卟啉二聚体

卟啉单体的直接偶合法. 这种方法包括有β-β, meso-β直接连接的二聚体[8,9]和直接连接的N混杂的卟啉二聚体[10]. 我们利用二环己烷基羰化二亚胺(DCC)作催化剂, 在冰盐浴条件下, 通过两个5-(p-羧基苯基)-10,15,20-三苯基卟啉(H2CPTPP)周边上的羧酸基团一步直接缩合获得以羧酸酐连接的新型卟啉二聚体. 利用多种光谱手段证实所合成的物质为目标产物. 该方法具有反应物单一、 反应步骤简单、 副反应少、 产物纯化方便、 时间短和产率高等优点.     

一种新型可光降解的PVC-OA-TiO_2纳米复合膜

采用包埋技术制备了一种新型可光降解的聚氯乙烯-草酸-TiO_2(PVC-OA-TiO_2)纳米复合膜,并研究了紫外光照射条件下该复合膜的光催化降解情况.结果表明,该纳米复合膜的光催化降解是一个氧化断链过程,经紫外光照射310 h后失重率达到55%,是PVC-TiO_2复合膜的2倍,是纯PVC膜的3.5倍,说明草酸的掺杂可以促进PVC-OA-TiO_2复合膜更快地被光降解.草酸作为一个良好的电子给体,能不可逆地与TiO_2表面产生的空穴或表面羟基反应,抑制电子和空穴的复合,从而显著提高PVC-OA-TiO_2的光催化降解速率.     

硅团簇结构和碎片行为的紧束缚理论方法

利用紧束缚分子动力学模拟退火方法研究了硅团簇Sin(n=2—14)的结构性质和能量.通过与前人工作结果(Si2—Si10)的比较,发现本理论方法的结果相当准确地再现了从头计算的结论.对较大的硅团簇所作的计算给出了有意义的结构预测.从能量观点出发,计算结果表明原子数分别为4,6,7,10,12和14的硅团簇较为稳定.还进一步研究了硅团簇的碎片行为,理论计算的结果表明较大的硅团簇的稳定碎片产物通常包括一个或两个“幻数”团簇