Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions

Reactions of CsI and HgI₂ with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)₂]₂[Hg₂I₆] (1) and {[Cs(15C5)]₂[Hg₂I₆]}_n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs⁺ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5) ₂ ⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5) ₂ ⁺ and anionic Hg₂I ₆ ^2- are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]₂[Hg₂I₆] units. Each structural unit contains two Cs(15C5)⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg₂I ₆ ^2- , and an iodine atom of Hg₂I ₆ ^2- in an adjacent structural unit. The interactions between the Cs⁺ of Cs(15C5)⁺ and an I^– in Hg₂I ₆ ^2- from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg₂I ₆ ^2- in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P2₁/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) Å, = 111.0(1)°, V = 3860 ų, Z = 4, R = 0.082 (R _w = 0.089). Crystal data for 2: space group P2₁/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) Å, = 91.54(3)°, V = 2146 ų, Z = 4, R = 0.034 (R _w = 0.048).     

Comparative Study of Carbon Paste,Screen Printed,and PVC Potentiometric Sensors Based on Copper‐sulphamethazine Schiff Base Complex for Determination of Iodide – Experimental and Theoretical Approaches

New poly vinyl chloride (PVC) membrane, carbon paste (CP), and screen printed (SP) electrodes are constructed for iodide sensing. They are based on copper (II)‐sulphamethazine Schiff base complex as suitable carrier. Mechanism was proved by FT‐IR and UV‐Vis spectroscopy. Computational study involving binding energies calculations at DFT/B3LYP level of theory confirmed the proposed mechanism and agreed the observed selectivity pattern. Responses are near‐Nernstian (?55.0, ?51.0 mV/concentration decade) for PVC, and SP electrodes, and super‐Nernstian (?61.2 mV/concentration decade) for the CP electrode. Lower limit of detection (3.2×10^?6 mol L^?1) and improved selectivity over the highly interfering thiocyanate were obtained in comparison with the previously reported Schiff base complexes‐based iodide sensors.     

A Polymeric Iodiplumbate(Ⅱ) Templated by Conjugated Quaternary Ammonium: Synthesis, Band Structure and Optical Properties

A new lead(Ⅱ) iodide coordination polymer [(npq)(PbI3)]n 1 (npq = N-propyl- quinolinium) has been synthesized in the presence of npq as structure-directing reagent (SDA). Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 19.158(4), b = 7.9909(16), c = 22.929(5) (A), V = 3510.2(12) (A)3, Z = 8, Dc = 2.877 g/cm3, F(000) = 2672, C12H14I3NPb, Mr = 760.14, μ(MoKα) = 14.872 mm-1, the final R = 0.0431 and wR = 0.1021 for 3678 observed reflections with I＞2σ(I). Structure determination indicates that the [PbI3]-n infinite chains in each unit cell shape the sketch of 1, which could be described as the result of face-sharing distorted PbI6 octahedra running along the b axis. Electrostatic interaction between conjugated organic counter-cations and inorganic moieties presents and contributes to the crystal packing. 1 was further characterized with IR and elemental analysis. Based on the crystal structure data, quantum chemical calculation with DFT method was used to reveal the electronic structure and optical property of 1.     

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.     

A study of preferential solvation of N-alkyl pyridinium iodides in mixed solvents containing acetonitrile

The charge transfer (CT) band maximum of N-alkyl pyridinium iodide (NAPI) has been studied as a function of the composition of binary mixed dipolar aprotic solvents. The deviation from linearity of the energy maximum (E₁₂) and the mole fraction (of a component solvent) plot is explained as due to a preferential solvation by the more polar cosolvent in the binary mixture. The extent of preferential solvation has been observed to vary with the composition, the maximum being towards the less-polar end. The role of hydrogen bond donating ability of a solvent in preferential solvation is discussed.     

金属锡作用下炔丙基碘与醛类化合物的反应

金属锡作用下的烯丙基卤代物与羰基化合物的加成反应以其反应条件温和及能选择性地与含有其他反应活性基团的羰基化合物加成等特点而显示出在有机合成上的应用价值。但目前这类反应还只局限于烯丙基卤代物反应的范围内。本文首次报道金属锡作用下的炔丙     

Ion chromatographic determination of iodide in urine and serum using a tubular ion-selective electrode based on a homogeneous crystalline membrane

The use of a laboratory-made iodide ion-selective electrode with tubular configuration and based on a crystalline membrane (AgI/Ag₂S) as the detector for ion chromatographic determination of iodide in urine and serum is described. A CIS reversed-phase column was coated withN-cetylpyridinium chloride to prepare a low-exchange-capacity analytical column and with hexadecyltrimethylammonium bromide to prepare a concentrator pre-column. A 2.0 ml min^–1 flow rate of deionized water and 0.1 mol 1^–1 KNO₃ solution was used for the pre-concentration and for the chromatographic separation, respectively. For optimum performance of the detector a background level of iodide was added into the column effluent. A linear relationship (r = 0.9997) between tubular electrode potential (as peak height) and iodide concentration in the range 5–400 g 1^–1 and a detection limit of 1.47 g 1^–1 were obtained. The method shows good reproducibility for both peak height (2.2% RSD) and retention time (1.3% RSD). Recoveries on its application to the samples were 93.0–100.9% for urine and 91.4–106.0% for serum.     

甲基锍盐的合成

在四氟硼酸银存在下，分别以硫醚、硫醇、硫酚或过硫醚为原料与碘甲烷反应制备了相应的甲基锍盐。用１ＨＮＭＲ和１３ＣＮＭＲ表征产物的结构并提出了反应的机理。     

Derivate von arsensubstituierten Phosphorchalkogeniden

Derivatives of Arsenic Substituted Phosphorus Chalcogenides α-AsP₃S₃I₂, α-AsP₃Se₃I₂, and three isomers of β-AsP₃S₃I₂ were observed besides several phosphorus sulfides by ³¹P NMR spectroscopy after the reaction of As_nP_4–nE₃ (E ? S; Se; n = 0–4) with I₂ in the melt or with I₂, PI₃, and N-iodosuccinimid in CS₂ solutions. The reaction of As_nP_4–nS₃ with CHI₃ in CS₂ solution yielded two isomers of β-AsP₃S₃(CHI₂)I.