YBO_3∶Eu中发光中心的格位与晶场拟合

通过对溶胶 凝胶法制备的YBO3∶Eu的光致发射谱进行分析 ,证实Eu3 可能占据两种晶场格位。并采用晶场拟合的方法定量确认这两种晶场格位的对称性分别为C3v和D3,这种指认下能级的拟合结果以及点群选择律和实验结果相当吻合。     

基质中不同稀土离子晶场强度的比较分析

用计入电荷屏蔽作用后的晶场参数关系式, 比较分析了两种典型的激光材料激活离子Er3+和Nd3+在一系列晶体基质中的标量晶场强度. 理论上得到两者之间的比值为0.761, 从实验数据中得到的相应比值为0.731±0.017, 理论计算结果和经验关系式符合得相当好. 由此可以得到当不同稀土离子在同一种基质材料中占据相同的格位时, 其晶场强度的比值.     

纳米晶ZrO2:Sm3+的制备与发光性质研究

用化学共沉淀法制备了Sm3 掺杂浓度不同、煅烧温度不同的纳米晶ZrO2:Sm3 系列发光粉体,所制备的粉体均具有Sm3 离子特征强室温荧光发射.通过XRD分析发现:经600℃煅烧2 h后制备的纳米晶ZrO2:Sm3 是四方相结构;经800℃煅烧2 h得到的样品,以四方相为主,有少量单斜相;经950℃煅烧2 h后得到的样品,以单斜相为主,四方相的比例较小.不同煅烧温度下样品发光性质研究表明:因经不同温度煅烧制备的样品所处晶体场环境不同,发光中心也不同,经800和950℃煅烧的样品中稀土离子占据两种不同的格位,其一为四方相格位,其二是单斜相格位;ZrO2基质与Sm3 之间有能量传递,单斜相结构更有利于能量传递.荧光强度与掺Sm3 浓度关系研究表明:荧光强度先随Sm3 浓度提高而增强,在浓度达0.7%(摩尔分数)时达到最大,然后又随之降低.     

三斜相GdBO3:Eu的溶胶-凝胶法制备及其格位选择激发下的光谱

用溶胶-凝胶法合成了具有三斜结构的低温相GdBO3,并与用常规的固相反应制备的类球方解石结构的样品作了比较.在高于1000℃时发生了三斜相向常规相的相变.三斜相GdBO3:Eu的荧光光谱表明阳离子在基质晶格中占据了两种格位,用A和B来分别标明.选择激发A、B格位上Eu3+,结果揭示了GdBO3结构上的变化和Eu3+之间的能量传递过程.在较高的Eu3+掺杂浓度时,两个格位均有较强的发光;在低温和低浓度条件下,得到了可分辨的相应于不同格位的发光,并观察到了两个格位间不同几率的能量相互传递.     

Eu~(3 )在CaYBO_4中的取代和发光

用固相法制备化合物CaY1 -xBO4∶xEu ,研究Eu3 在CaYBO4中的取代格位和发光特性。当Eu3 掺杂浓度不大时 ,存在两个发光中心 ,认为是取代基质中有两个Y格位的结果 ;通过对Eu O的电荷迁移激发带位置的分析 ,表明Eu3 所处八面体中心格位的对称性越低 ,Eu O的电荷迁移带越偏向于短波 ;当Eu3 的掺杂浓度较大 (x >0 1 0 )时 ,Eu3 离子也可占据Ca2 格位 ,同时Eu3 还原成Eu2 。     

La2CaBl0O19：Ce3＋在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19:Ce3 在VUV-Vis范围的光谱，发现Ce3 在La2CaBl0O19中共有两种格位．分别取代了十配位的La3 和八配位的Ca2 ．从而发射光谱中没有出现特征的双峰。而出现了峰值约位于307．330和356nm的3个发射峰．由于在低对称性晶体场中d轨道的分裂．激发光谱中位于194，224,243,260,274和318nm的峰是由两个格位的Ce3 的f-d跃迁引起的．Ce^3 占据两个格位．可以通过以Eu3 为荧光探针的发射光谱中出现的两个5Do-7Fo跃迁得到验证．峰值位于162nm的激发谱带是基质吸收带．与基质禁带宽度相对应．通过计算．不排除其中包含O2-→Ce3 的电荷迁移带的可能性．     

C_(3v)晶场中d~3离子吸收谱的理论研究

为了计算Cr~(3+)离子在C_(3v)对称晶场中的能谱,本文采用一种形式介于Richardson和Watson SCF波函数之间的束缚态d电子径向轨函;从Oh点群的Griffith标准基出发,用一种简便的方法,推出d~3系的C_(3v)点群强场谱项能量矩阵。由此计算了Ruby(Al_2O_3+Cr~(3+))和Cr_2O_3晶体中Cr~(3+)离子的吸收谱。在考虑扳——电耦合后,理论结果与实验符合甚好,从而解释了这两类晶体中Cr~(2+)吸收光谱的机制。这种计算方法既使拟合参数的数目大为减少,又使配位场理论计算格地理论化。     

论络合物中心过渡金属离子的径向波函数

考虑中心对称配体场影响,提出一种不同基混合的束缚态过渡金属离子的3d径向波函数。利用这种波函数,计算了一些Cu⁺⁺络离子的晶场谱。假设适当的边界条件,用一个拟合参数,就能得到和实验一致的结果。这种方法的实质在于,在晶体场静止点荷模型基础上,考虑了诸配体等效中心对称场的部份分子轨道效应。这种混合基单电子3d径向波函数也能用于完全的分子轨道理论计算。     

La_2CaB_(10)O_(19):Ce~(3+)在VUV-Vis范围的发光性质研究

通过研究La_2CaB_(10)O_(19):Ce~(3+)在VUV-Vis范围的光谱.发现Ce~(3+)在La_2CaB_(10)O-(19)中共有两种格位.分别取代了十配位的I。a’“和八配位的Ca”,从而发射光谱中没有出现特征的双峰,而出现了峰值约位于307,330和 356 nm的3个发射峰.由于在低对称性晶体场中d轨道的分裂.激发光谱中位于194.224,243.260,274和318 nm的峰是由两个格位的Ce~(3+)的f-d跃迁引起的.Ce~(3+)占据两个格位,可以通过以Eu~(3+)为荧光探针的发射光谱中出现的两个~5D_(0-)~7F_0跃迁得到验证.峰值位于162 nm的激发谱带是基质吸收带.与基质禁带宽度相对应.通过计算,不排除其中包含O~(2-)→Ce~(3+)的电荷迁移带的可能性.     

La2CaB10O19∶Ce3+在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19∶Ce3+在VUV-Vis范围的光谱, 发现Ce3+在La2CaB10O19中共有两种格位, 分别取代了十配位的La3+和八配位的Ca2+, 从而发射光谱中没有出现特征的双峰, 而出现了峰值约位于307, 330和356 nm的3个发射峰.由于在低对称性晶体场中d轨道的分裂, 激发光谱中位于194, 224, 243, 260, 274和318 nm的峰是由两个格位的Ce3+的f-d跃迁引起的.Ce3+占据两个格位, 可以通过以Eu3+为荧光探针的发射光谱中出现的两个5D0-7F0跃迁得到验证.峰值位于162 nm的激发谱带是基质吸收带, 与基质禁带宽度相对应.通过计算, 不排除其中包含O2-→Ce3+的电荷迁移带的可能性.     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

γ-Nitro-γ-butyrolacton

γ-Nitro-γ-butyrolactone By oxidation of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) with KMnO₄, besides 3-(1′-nitro-2′-oxocyclohexyl)pripionic acid ( 2 ), the complete hydrolysis product 4-oxononanedioic acid ( 4 ) and the oxidized semi-hydrolysis product 5-(2-nitro-5-oxotetrahydro-2-furyl)pentanoic acid ( 3 ) were formed. The crystalline 3 decomposes at r.t. forming 4 and nitrous gases; its structure was established by X-ray determination.     

Synthesis of γγγ-trifluorocarbonyl compounds

γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF₃-CH₂-) on the -methylene group of a ketone.     

K3SbSe3, Rb3SbSe3 und Cs3SbSe3 – Synthese und Kristallstruktur

K₃SbSe₃, Rb₃SbSe₃, and Cs₃SbSe₃ – Synthesis and Crystal Structure The compounds K₃SbSe₃, Rb₃SbSe₃ and Cs₃SbSe₃ were synthesized by heating mixtures of Sb₂O₃ and an alkalicarbonate in a stream of hydrogen saturated by selenium in a temperature range between 750 °C and 800 °C. The compounds crystallize isostructural with Na₃AsS₃. A comparison of atomic distances and bond angles with those of the isostructural arsenic and bismuth compounds shows the effect of lone pairs.     

Freezing the polarization of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite films

Thin films of methylammonium lead halides, CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, were deposited onto symmetrical microstructured electrode arrays of gold or platinum on Si/SiO₂ wafers. Polarization studies were carried out on perovskite films under vacuum in the dark. For poling, a constant voltage was applied to the samples while the temperature was cycled between 295 K and 4 K. The measured current densities depending on the temperature showed distinct characteristics relating strongly to the crystal phase and the dielectric properties of the perovskite films. Voltage sweeps were carried out at different scan rates at specific temperature intervals after poling. The polarization of the films due to the migration of iodide vacancies in direction of the blocking perovskite/metal interface was frozen almost up to room temperature. Charge carriers were only able to cross the blocking barrier and contribute to the current where the ions have accumulated during poling. All J-V curves showed hysteresis: inverted and regular hysteresis at room temperature and below, respectively. Inverted hysteresis originates from the slow accumulation of ions at the blocking barrier, while regular hysteresis arises from a distortion in the adjacent crystals which will be discussed.     

Synthesis of some derivatives of 3-amino-3-desoxyerythrose and 3-amino-3-desoxy-D-3-erythrose

The synthesis of derivatives of 3-amino-3-deoxy-L-erythrose by LAH or LAD reduction of the oxime of 1,2-O-isopropylidene α-L -glycero-tetros-3-ulofuranose is described.     

3x-pyrrolizin-3-ones

Condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groups, in the KOH-DMSO system, was used to prepare previously unknown 1-alkylthio-3H pyrrolizin-3-ones. The latter, treated with secondary amines, are readily converted to the corresponding 1-amino derivatives.     

3-H-pyrrolizin-3-ones

Previously unknown 1-alkylthio-3H-pyrrolizin-3-ones have been obtained by the condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groupings in the KOH-DMSO system. On treating the products with secondary amines they are readily converted into the corresponding 1-amino derivatives.Irkutsk Branch of the Russian Academy of Sciences, Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–924, July, 1996. Original article submitted May 2, 1996.