An Investigation on the Structure of Polyselenocyanogen [Se2(CN)2]x

The structure of polyselenocyanogen [Se₂(CN)₂] _x is analogous to that of polythiocyanogens, which have the general formula [S _y (CN)₂)] _x (y=1,2,3,...). This result is based on the surprising fact that the FT-IR spectrum of the former compound is similar to the spectra of the latter class of compounds and on other experimental data. Thus, the proposed structure for polyselenocyanogen involves polyazomethine chains connected together by selenium bridges. Selenocyanogen Se₂(CN)₂ polymerizes when treated with certain organic solvents. The polymerization was followed by electronic spectroscopy and involves the formation of peculiar absorption bands in the visible and near infrared portion of the spectrum. Alternatively, selenocyanogen polymerization is promoted by thermal treatment in high boiling solvents like xylenes and decalin. The resulting polymer shows an FT-IR spectrum comparable to that of polythiocyanogens. The thermal stability of selenocyanogen has been studied by thermogravimetric analysis (TGA) in conjunction with differential thermal analysis (DTA). Heating of Se₂(CN)₂ under N₂ to 650°C causes conversion into paracyanogen (CN) _x with the release of selenium.     

Properties and structure of (As2Se3)1 − z (SnSe)z − x(GeSe)x and (As2Se3)1 − z (SnSe2)z − x(GeSe2)x glasses

Two valence states of tin atoms in (As₂Se₃)_{1 ? z} (SnSe)_{z ? x}(GeSe)_x and (As₂Se₃)_{1 ? z} (SnSe₂)_{z ? x}(GeSe₂)_x glasses are identified by Mössbauer and photoelectron spectroscopy. It is demonstrated that the presence of doubly charged tin ions in the structural glass network does not give rise to impurity conduction or impurity optical absorption. The inference is made that these glasses can be treated as semiconductor solid solutions.     

Structure and catalytic activity of a hexarhenium cluster-supported copper cubanes [{Cu4(μ-OH)4(NH3)7}2{Re6Se8(CN)6}][Re6Se8(CN)6] · 2H2O

The first hexarhenium cluster-supported Cu₄(OH)₄ cubanes had been synthesized. The complex displayed a belt-like one-dimensional structure with dangling Cu₄ cubanes. As a heterogeneous catalyst, the complex showed a high catalytic activity in the transesterification of a range of esters with methanol under the mild conditions. Moreover, it can be reused without any loss of activity through five runs with ester, which suggests that this catalyst is an efficient, mild, and easily recyclable one for the alcoholysis of esters.     

配合物[Cu（L）2]ECu’（L）2]·CH3OH·3H2O的合成和结构表征

以邻氯蜷苯磺酸与吡啶-2-甲醛进行缩合得到席夫碱配体（KL）,然后与Cu（AeO）2．H20进行配位反应,得到了席夫碱配合物[Cu（L）2][Cu’（L】2】’CH3OH·3H2O,用面素分析、FT—IR和X-射线单晶衍射进行r表征。结果表明t配合物属]i单斜晶系,P21／c空间群。配合物的一一个独立单元由置个品格水分子、一个晶格甲醇分子和两个不同的单核铜单元构成。有趣的是,这两个荤核铜单元的组成完全相同但配位模式不同,它们均由一个铜离子和两个脱质子的席夫碱配体组成,其中一个瞥核铜单元中的两个磺酸基均参与了配位,另一个则只有一个磺酸基配位。     

氰桥化合物[cis-Fe(bpy)2(CN)2Mn(L)]2[PF6]4的合成及其对金属离子选择识别作用

将Mn(Ⅱ)离子、有机配体L(L=1,6-二苯基-2,5-双(2-甲基吡啶基)-2,5-二重氮己烷)和氰基化合物cis-FeⅡ(bpy)2(CN)2·3H2O(bpy=2,2′-联吡啶)在NH4PF6存在下制备一个四元环异核氰桥化合物即标题化合物,并对其结构进行表征。重金属离子对标题化合物的荧光响应研究表明,标题化合物对Cu(Ⅱ)和Fe(Ⅲ)有很好的选择性。随着金属离子Cu(Ⅱ)和Fe(Ⅲ)的加入,标题化合物的荧光强度逐渐降低至基本消失。随着金属离子Pb(Ⅱ)和Fe(Ⅱ)的加入,标题化合物的荧光强度逐渐降低,当金属离子加到一定浓度,标题化合物的荧光强度不随金属离子的变化而变化。对于Co(Ⅱ)、Cr(Ⅲ)、Mn(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)等离子,随着金属离子的加入标题化合物的荧光强度改变甚微或不改变。     

[(C_2H_5)_4N]_2｛Fe_4S_4[S_2CN(C_2H_5)_2]_4｝的晶体和分子结构

本文报导含类立方烷型簇核Ｆｅ４ｓ４的金硫配位化合物［（Ｃ２Ｈ５）４Ｎ］２｛Ｆｅ４Ｓ４［Ｓ２ＣＮ（Ｃ２Ｈ５）２］４｝的合成、晶体和分子结构测定的结果。     

Two-equivalent electrochemical reduction of a cyano-complex [Tl(CN)2] and the novel di-nuclear compound [(CN)5Pt−Tl]

Extending our recent insights in two-electron transfer microscopic mechanisms for a Tl^III/Tl^I redox system [D.E. Khoshtariya, et al., Inorg. Chem. 41 (2002) 1728], the electrochemical response of glassy carbon electrode in acidified solutions of Tl^III (ClO₄)₃ containing different concentrations of sodium cyanide has been extensively studied for the first time by use of cyclic voltammetry and the CVSIM curve simulation PC program. The complex [Tl^III(CN)₂]⁺ has been thoroughly identified electrochemically and shown to display a single well-defined reduction wave (which has no anodic counterpart), ascribed to the two-equivalent process yielding [Tl^I(aq)]⁺. This behavior is similar to that of [Tl^III(aq)]³⁺ ion in the absence of sodium cyanide, disclosed in the previous work, and is compatible with the quasi-simultaneous yet sequential two-electron transfer pattern (with two reduction waves merged in one), implying the rate-determining first electron transfer step (resulting in the formation of a covalently interacting di-thallium complex as a metastable intermediate), and the fast second electron transfer step. Some preliminary studies of the two-equivalent reduction of directly metal-metal bonded stable compound [(CN)₅Pt^II-Tl^III]⁰ has been also performed displaying two reduction waves compatible with a true sequential pattern.     

铁磁—亚铁磁合金磁体(Ni_xMn_(1-x))[Cr(CN)_6]制备和结构

采用化学合成的方法制备了分子基合金磁体(Ni_xMn_(1-x))_(1.5)[Cr(CN)_6],X-射线分析表明,制备的分子基合金磁体具有面心立方结构,晶格常数随Ni的成分x的增加而减小,红外光谱(IR)分析显示Cr-CN的键的特征随Ni的成分x的变化而改变。     

Radiation stability of tin charge states in the (As2Se3)1−z (SnSe) z − x (GeSe) x glasses

This paper reports on the results of investigations into the radiation stability of tin charge states in the (As₂Se₃)_1?z (SnSe) _{z ? x} (GeSe) _x glasses. It is revealed using ¹¹⁹Sn Mössbauer spectroscopy that gamma irradiation of the (As₂Se₃)_1?z (SnSe) _{z ? x} (GeSe) _x glasses leads to partial oxidation of doubly charged tin ions with the formation of the amorphous (finely dispersed) SnO₂ phase blocked by the glass. As a result, the physicochemical properties (density, microhardness, glass transition temperature, activation energy for electrical conduction) of the glasses exposed to gamma irradiation remain virtually unchanged.     

[Ru(CN)_6]~(3-)在溴碘化银T-颗粒乳剂中的掺杂

研究了K4犤Ru(CN)6犦掺杂剂对溴碘化银T-颗粒乳剂感光性能的影响,结果表明掺杂剂的掺杂量以及掺杂位置对乳剂的感光性能都有影响。当K4犤Ru(CN)6犦的掺杂量为3.1×10-8～3.1×10-9mol/g乳剂之间时,掺杂剂掺杂在乳剂的任意位置,乳剂感光度都有提高,表明K4犤Ru(CN)6犦是浅电子陷阱掺杂剂。掺杂位置接近表面或接近内核时效果相对较好,最佳的掺杂量为3.1×10-8mol/g乳剂。当掺杂剂的掺杂量小于3.1×10-10mol/g乳剂,且掺杂位置接近富碘区时,乳剂的感光度反而下降。     

[Ru(CN)_6]~(4-)在溴碘化银立方体乳剂中的应用

研究了[Ru(CN)6]4-在溴碘化银立方体乳剂中的掺杂,[Ru4(CN)6]4-作为1种浅电子陷阱掺 杂剂可有效地改善乳剂的感光性能。通过实验确定了最佳掺杂位置和用量,并从理论上进行了初步探讨。     

The Influence of Gamma Irradiation Dose on the Formation of Radiation Defects in xCu2Se · (1 – x)As2Se3 Glasses

The defects generated under exposure to gamma radiation at a temperature of 77 K in glasses lying along the xCu₂Se · (1 – x)As₂Se₃ quasi-binary join are studied by the electron paramagnetic resonance (EPR) method. The intensity of EPR signals (I) of radiation-induced defects associated with dangling bonds of atoms in the glass network is examined as a function of the gamma irradiation dose (D = 10⁴–1.5 × 10⁵ Gy). Unlike the As₂Se₃ glass, for which the signal intensity increases almost linearly with an increase in the irradiation dose, the curves I(D) for ternary glasses are characterized by saturation dependent on the copper content in the network. The saturation of the dependences I(D) at a high copper content is explained by the formation of regions with an increased Cu content and the enhancement of the electron–phonon interaction, which prevents the stabilization of dangling bonds in the glass network. The concentration of NO₂ paramagnetic molecules formed by nitrogen and oxygen uncontrollable impurities increases linearly with an increase in the irradiation dose.     

氢键配合物[Mn(H_2O)_2(HNic)_2]晶体的合成及结构表征

用3d金属离子锰与2-羟基-3-吡啶羧酸配体合成出新的水杨酸式螯合具有三维网络结构的Mn(H_2O)_2(HNic)_2配合物。均三苯甲酸苯环上一、三、五位置上的羧基都有脱质子化进行各种不同的结合,利用这点水溶液合成氢键配合物Mn(H_2O)_2(HNic)。我们采用常规分析方法即元素分析谱等,对配合物进行了表征.利用X-射线衍射晶体结构分析,结果显示该配合物属于单斜晶系,空间群为P2(1)/c,每一各晶胞包含两个Mn(H_2O)_2(HNic)_2分子,一个2-羟基-3-吡啶羧酸分子,通过N原子质子化的H原子与临近2-羟基-3-吡啶羧酸分子上的羟基上O原子又形成了一个八元环的氢键结构,该配合物具有复杂的氢键结构。     

[Ru(CN)_6]~(4-)在溴化银立方体乳剂中的应用

研究了 [Ru (CN) 6]4-在溴化银立方体乳剂中的掺杂 ,[Ru4(CN) 6]4-作为 1种浅电子陷阱掺杂剂可有效地改善乳剂的感光性能。通过实验确定了最佳掺杂位置和用量 ,并从理论上进行了初步探讨。     

配合物[Cd(IA)_2(H_2O)_4]的合成及晶体结构

以硝酸镉与吡啶-4-甲酸(HIA)为原料在水热条件下合成了配合物[Cd(IA)2(H2O)4],并用红外光谱、元素分析和X射线单晶衍射进行了表征。该配合物属三斜晶系,P-1空间群,晶胞参数为:a=6.4400(5)nm,b=6.9489(6)nm,c=9.4051(8)nm,α=95.2600(10)°,β=104.580(2)°,γ=111.570(2)°,V=0.037079(5)nm3。配合物中Cd(Ⅱ)位于变形八面体环境中,与分属于两个吡啶-4-甲酸根的2个N原子以及来自于四个配位水分子的O原子配位。     

Thermo-structural characterization of (As2Se3)100-x-(As2Te3)x glasses for infrared optics

Differential scanning calorimetry was used to study thermokinetic behavior of (As₂Se₃)_100−x(As₂Te₃)_x infrared glasses (seven compositions along the pseudo-binary were investigated). Glass-transition kinetics was described in terms of the Tool-Narayanaswamy-Moynihan model and the relaxation motions were interpreted using Raman spectroscopy data. The enthalpy relaxation kinetics was found to be absolutely uninfluenced by changing Se/Te ratio. On the other hand, DSC crystallization behavior changed significantly with increasing As₂Te₃ content: Te-rich compositions show marked affinity toward crystallization, whereas in case of the compositions with 0-34 mol.% As₂Te₃ crystal growth is significantly suppressed. X-ray diffraction analysis indicated presence of monoclinic As₂Se₃, As₂Te₃, and As₂Se(Te)₃ phases. The complex crystallization behavior occurring in case of the Te-rich compositions was described by superposition of two autocatalytic kinetic signals. Based on the information from infrared microscopy the two overlapping crystallization processes can be attributed to the respective formations of spherulitic and needle-shaped crystallites. Best glass stability was identified in case of the (As₂Se₃)₆₆(As₂Te₃)₃₄ composition, which appears to be a potential candidate for optic applications in the far-infrared region of the spectrum.     

Synthesis,structure, and thermal behavior of [Cu70Se35(PEt2Ph)24]

We investigated the molecular and crystal structure as well as the thermal behavior of [Cu₇₀Se₃₅(PEt₂Ph)₂₄] using single-crystal X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), X-ray powder diffractometry, and thermal gravimetric analysis (TGA). The use of a He-cooled sample head in HRTEM makes possible for the first time the investigation of semiconductor cluster molecules under the extreme conditions of the experiment and, thus, comparison with the results of single-crystal X-ray diffraction. The lattice spacings and packing symmetry of the three-dimensional cluster molecule superlattice found in HRTEM are in good agreement with the ones determined by X-ray structure diffraction. The atomic ordering inside the cluster molecules, which resembles a hexagonal packing of the selenium atoms, could not be resolved in the HRTEM measurements, since upon irradiation with the electron beam the clusters start to move after a few seconds and the images go out of focus. This movement is possibly affected by cleavage processes of the phosphine ligands, as could be observed in thermal gravimetric analysis under comparably mild conditions. Powder diffraction measurements show that this cleavage of ligand molecules is accompanied by the formation of larger copper selenide cluster cores and ends up at high temperatures in the formation of bulk α-Cu₂Se.     

S-二苯基脯氨醇三乙基硅醚制备方法的改进

以手性S-二苯基脯氨醇及三乙基硅基三氟甲烷磺酸酯为原料,在三乙胺存在下缩合成手性醚类化合物二苯基脯氨醇三乙基硅醚。通过高效液相色谱法测定目标产物的纯度为96%,产率为79.2%,该方法产品纯度高,操作简便。     

2-氨基嘧啶超分子配合物[Cu(2-AP)2(NO3)2]的合成与晶体结构

以2-氨皋嘧啶缩水杨醛席夫碱和硝酸铜为原料,在常温下,用甲醇和水为溶剂合成了配合物[Cu（2,Ap）2（NO3）2]（2-Ap=2,氨基嘧啶）。通过红外光潜、元素分析、X-射线单品衍射对它进行了结构解析和表征,并系统研究了配合物的结构特点。