基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)和2,2′-联吡啶(L₂)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO₄·7H₂O)、六水合硝酸钴(Co(NO₃)₂·6H₂O)分别反应,得到配合物[Zn(L₁)(L₂)(H₂O)]_n(1)和配合物[Co(L₁)(L₂)(H₂O)]_n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn²⁺配位连接L^2-₁与L₂形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1ⁱ离子由H₂L₁上的羧酸氧原子O4和O4ⁱ连接,形成双齿螯合的配位结构单元,以Co²⁺配位连接 L^2-₁和L₂形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。     

Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Characterization of ZnO:AI films deposited by r.f.magnetron-sputtering at low temperature

Transparent conducting ZnO:AI thin films with good adhesion and Iow resistivity have been prepared on organic substrates and Coming 7059 glass substrates by r.f. magnetron-sputtering technique at Iow substrate temperature (25-210℃). Structural and photoelectric properties of the deposited films are investigated. The deposited films are polycrystalline with hexagonal structure and a preferred orientation with the c-axis perpendicular to the substrate. Only the (002) peak is observed.High quality films with resistivity as Iow as 1.0 x 10- 3Ω@ cm and 8.4 x 10- 4Ω@ cm, the average transmittance over 74% and 85% in the wavelength range of the visible spectrum have been obtained on different substrates.     

Characterizations of Tb:Zn2SiO4 films on silicon wafer prepared by sol-gel dip-coating and solid-phase reaction

Terbium-doped Zn_2SiO_4 films were successfully prepared on Si wafers by a simple sol-gel dip-coating and solid-phase reaction method of ZnO and SiO_2. X-ray diffraction (XRD) and UV－Vis absorption results revealed that films processed below 850℃ were ZnO in wurzite structure, and films processed above 850℃ were Zn_2SiO_4 in wellimite structure. Photoluminescence measurements of the Tb-doped Zn_2SiO_4 films showed two strong emission bands at 490 and 545nm. The photoluminescence lifetime was 4.6ms.     

Zn(BTZ)2白色有机电致发光材料的合成及其器件制备

以PCl₃为脱水剂,将邻氨基硫酚与水杨酸脱水环化合成出2-(2-羟基苯基)苯并噻唑,并进一步将所得产物与乙酸锌反应合成出2-(2-羟基苯基)苯并噻唑螯合锌(Zn(BTZ)₂)材料。以该配合物作为发光层制备出结构为ITO/PVK:TPD/Zn(BTZ)₂/Al近白色电致发光器件,其色坐标位于白场之内(x=0.242,y=0.359),在驱动电压为16V时,亮度达3200cdm²,对应的量子效率为0.32%。进一步在Zn(BTZ)₂中掺入橙红色染料Rubrene,制成ITO/PVK:TPD/Zn(BTZ)₂:Rubrene/Al结构器件,实现了纯白色发光(色坐标值:x=0.324,y=0.343),非常接近于白色等能点,且量子效率达0.47%。最后对上述器件的发光和电学性能进行了深入的研究和探讨。     

Influence of radiation on thin ZnS-Tb films

Changes in thin zinc-sulfide films under the action of the γ-radiation of Co⁶⁰ are studied by investigating electroluminescence spectra of terbium embedded in these films as a luminescent probe. It is shown that changes in the relation of the intensities of bands, a decrease in their halfwidth and the background component, and simplification of the spectrum are observed in a short-wave region of the Tb radiation spectrum that corresponds to⁵D₃→⁷F_j transitions. The same modification of the radiation spectrum is characteristic of ZnS films whose crystalline structure is ordered in the course of thermal annealing at a temperature of 350°C. Based on the analysis of the data obtained it is inferred that irradiating the ZnS films with small radiation doses of 10⁴–10⁵ rad leads to the ordering of their crystalline structure due to the elimination of one of the types of structural defects. Institute of Physics of Semiconductors, National Academy of Sciences of Ukraine, 45, Nauka Ave., Kiev-28, 252650. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 338–341, May–June, 1997.     

生物小分子与铜锌超氧化物歧化酶相互作用的波谱学研究及其应用

本工作以ESR和NMR为主要手段,并结合其它生化方法,考察了氨基酸、核酸碱基、糖等生命基本物质,和抗坏血酸等生命必需物质与钢锌超氧化物歧化酶的相互作用,实验观测到氨基酸、核酸碱基和抗坏血酸在水溶液中可以与酶中的Cu²⁺作用而使其脱离活性部位,以小分子络合物形式游离在溶液中,同时使酶失活,脱离活性部位的Cu²⁺的比例和酶的失活程度取决于小分子配体的加入量及其与Cu²⁺的络合能力。此外,首次尝试使用ESR方法,并借助氨基酸与酶的作用,考察了铜锌超氧化物歧化酶在盐酸胍变性和热变性过程中的构象变化行为,结果表明这一方法是直观而有效的。     

57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

The origin of the formation of cavities in galvanized coatings

The role of water‐soluble corrosion products on galvanized wires was examined. The samples used were industrial hot‐dip galvanized wires, which were exposed to the open air under all weather conditions for a relatively short time (6 and 12 months), in an urban environment close to the sea. The samples were studied by different methods, i.e. scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and optical microscopy (OM). Several phases were detected because of the galvanization procedure and the steel substrate. Furthermore, phases which were formed as a result of the reaction of zinc with the atmosphere were also detected. These were oxides like ZnO, carbonates like ZnCO₃ and hydrated Zn and Fe sulfates. Their presence influences the corrosion resistance of the wires, which finally, strongly depends on the solubility of the wires in water. The SO₄^2? compounds especially are very soluble and consequently are easily removed from the coating surface, leading to its degradation by the formation of cavities. In any case, their presence, even after a short period of exposure, implies that the coating is highly affected by the atmosphere of the modern city. Copyright © 2006 John Wiley & Sons, Ltd.     

两种以Znq2为基体的新型电致发光材料的合成与性能

以8-羟基喹啉为配体的金属配合物是一种性能优良的有机电致发光材料,其中有关8-羟基喹啉铝(Alq₃)研究已有大量报道,8-羟基喹啉锌(Znq₂)研究还有待发展。介绍了两种以Znq₂为基体的新型有机电致发光材料Znq₂(H₂O)₂和(Znq₂)₄的合成方法。用IR、XRD、TG、DTA和荧光测试方法进行表征与分析表明:Znq₂(H₂O)₂和(Znq₂)₄的玻璃化温度(T_g)分别为104.2℃和204.9℃;在161℃下Znq₂(H₂O)₂脱去水分子成为Znq₂,在361℃高温下四聚体(Znq₂)₄裂解为单体Znq₂;Znq₂(H₂O)₂和(Znq₂)₄具有很好的发光性能,在光致发光谱中λ_max分别是505,550nm。