Structure determination of zinc iodide complexes formed in aqueous solution

Structures of the complexes formed in aqueous solutions between zinc(II) and iodide ions have been determined from large-angle X-ray scattering, Raman and far-IR measurements. The coordination in the hydrated Zn²⁺ hexaaqua ion and the first iodide complex, [ZnI]⁺, is octahedral, but is changed into tetrahedral in the higher complexes, [ZnI₂(H₂O)₂], [ZnI₃(H₂O)]^– and [ZnI₄]^2–. The Zn-I bond length is 2.635(4)Å in the [ZnI₄]^2– ion and slightly shorter, 2.592(6)Å, in the two lower tetrahedral complexes. In the octahedral [ZnI(H₂O)₅]⁺ complex the Zn-I bond length is 2.90(1)Å. The Zn-O bonding distances in the complexes are approximately the same as that in the hydrated Zn²⁺ ion, 2.10(1)Å.     

对一个大单轴磁各向异性镍(Ⅱ)配合物中的磁跃迁的直接观察

最近Ruamps和同事发现三角双锥构型的Ni（Ⅱ）配合物[Ni（Me₆tren）Cl]ClO₄（1，Me₆tren=tris（2-（dimethylamino）ethyl）amine）具有大的单轴磁各向异性（J.Am.Chem.Soc.，2013，135：3017-3026）。他们利用HF-EPR研究获得横向零场分裂（ZFS）参数E=1.56（5）cm^-1但未能确定轴向零场分裂参数D。在本工作中，我们利用0~17.5 T和5 K的变磁场远红外光谱（FIRMS）来检测自旋基态S=1中的M_S=±1和M_S=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁，得出轴向ZFS参数D=-110.7（3）cm^-1。我们对1的晶体结构进行了Hirshfeld表面分析，揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。     

Vibrational Spectroscopic Studies on the Dicyclopropylaminecadmium(II)Tetracyanometallate(II) Benzene Clathrates

ABSTRACT

New Hofmann–T_d-type clathrates of the forms Cd(CPA)₂M(CN)₄.C₆H₆ (CPA = cyclopropylamine; M?Cd or Hg) prepared in powder form and characterized by FT-IR, FT-Raman, far-IR spectra, X-ray diffraction, and elemental analyses are reported. Vibrational assignments are proposed for the bands of the host lattice and guest molecule. It is shown that the spectra are consistent with a proposed crystal structure for the compounds derived from X-ray diffraction measurements. The C, H, and N analyses were carried out for all the compounds. All the vibrational modes of coordinated CPA are characterized. The spectral features suggest that these compounds are similar in structure to the Hofmann–T_d-type clathrates.     

Pyridin type complexes of transition-metalhalides

A large number of Co-picoline-chlorides were prepared from different reaction media by changing the Co: picoline molar ratio.A new solid-gas phase method is described to prepare ternary mixed Co-picoline complexes containing different picolines.According to the thermal and spectral investigations the ligand chemisorption from the vapour phase depends on the stability of the solid complex and the complex formation ability of the ligand in the gas phase.

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Zusammenfassung In verschiedenen Reaktionsmedien wurden unter Änderung des Co: Pikolin Verhältnisses eine große Anzahl verschiedener C-Pikolinchloride hergestellt.Es wird eine neue Fest-Gas-Phasenmethode zur Herstellung ternärer Co-Pikolinmischkomplexe mit verschiedenen Pikolinen beschrieben.Entsprechend den thermischen und spektralen Untersuchungen hängt die Chemisorption der Liganden aus der Dampfphase von der Stabilität des festen Komplexes und vom Komplexbildungsvermögen des Liganden in der Gasphase ab.

     

Construction of Ternary Iodine–Bromine–Chlorine Octahalides

A series of five ternary octanuclear iodine-bromine-chlorine interhalides, [I₂Br₂Cl₄]²⁻ ( 1 ), [I₃BrCl₄]²⁻ ( 2 ), [I₄Br₂Cl₂]²⁻ ( 3 ), [I₂Br₄Cl₂]²⁻ ( 4 ) and [I₃Br₃Cl₂]²⁻ ( 5 ), have been rationally constructed in two steps. Firstly, addition of a dihalogen (ICl or IBr) to the triaminocyclopropenium chloride salt [C₃(NEt₂)₃]Cl forms the corresponding trihalide salt with [ICl₂]⁻ or [BrICl]⁻ anions, respectively. Secondly, addition of a half-equivalent of a second dihalogen, followed by crystallization at low temperature, gives the corresponding octahalide: addition of Br₂ and IBr to [ICl₂]⁻ gives 1 and 2 , respectively, whereas addition of I₂, Br₂ and IBr to [BrICl]⁻ gives 3 , 4 and 5 , respectively. The five octahalides were characterized by X-ray crystallography and far–IR spectroscopy.     

两种半乳糖醇氯化钆配合物的制备与表征

与羟基配位是金属离子的一种重要的存在形式. 我们得到了两种半乳糖醇氯化钆配合物, 其中一种为金属离子与配体为2:1的配合物,钆离子与半乳糖醇的三个羟基及六个水分子配位, 其它水分子以结晶水的形式存在, 氯离子不参加配位;另一种配合物根据红外, 元素分析, 差热热重, 远红外以及太赫兹光谱推测可能是钆离子与两个半乳糖醇分子的六个羟基以及三个水分子配位, 形成1:1配合物. 实验结果说明半乳糖醇与稀土离子之间可以形成多种配合物, 金属离子与糖的羟基存在着复杂的相互作用.     

同步辐射红外光谱技术在生物医用领域的应用

同步辐射作为一种新型红外光源,具有光谱宽、亮度高、分辨率高的特性,在生命科学领域具有广泛的应用。随着同步红外显微镜成像技术的不断发展,同步辐射红外光谱技术可以在原位探测亚细胞级别的生物化学变化,并保留细胞的生命特征。通过对蛋白质、核酸、磷脂等成分的定性和定量分析,可以了解骨细胞、神经细胞的病变,癌变细胞的活动情况以及植物细胞的营养状况等。同时,同步辐射红外光谱技术的应用范围正在不断扩展,其在药物释放的检测和生物化学过程的监控等方面也具有相当的应用前景。此外,在生物分子的分子间振动能级所处的远红外区,同步辐射红外光谱相比于常规红外光谱具有较高的信噪比。     

Primary aliphatic amine complexes of transition-metal halides

The hexakis(methylamine) complexes of nickel(II)-chloride, -bromide and -iodide have been prepared using-gas phase preparation procedure. The thermal decomposition starts with the release of four moles of the organic ligand. The bis(methylamine) intermediate decomposes in one step to the pure nickel(II) halide in the case of the chloride compound, however one and a half moles of methylamine containing intermediates were identified for the bromide and iodide analogues. The UV/VIS and the far IR spectra of the hexakis complexes show a typical octahedral environment around the central nickel(II) ion.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday