Bis(hinokitiolato)copper(II): modification (III)

Bis(hinokitiolato)copper(II), Cu(hino)₂, exhibits both antibacterial and antiviral properties, and has been previously shown to exist in two modifications. A third modification has now been confirmed, namely tetrakis(μ₂‐3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)tricopper(II)–bis(μ₂‐3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)bis[(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)copper(II)] (1/1), [Cu(C₁₀H₁₁O₂)₂]₃·[Cu(C₁₀H₁₁O₂)₂]₂, where 3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olate is the systematic name for the hinokitiolate anion. This new modification is composed of discrete [cis‐Cu(hino)₂]₂[trans‐Cu(hino)₂] trimers and [cis‐Cu(hino)₂]₂ dimers. The Cu atoms are bridged by μ₂‐O atoms from the hinokitiolate ligands to give distorted square‐pyramidal and distorted octahedral Cu^II coordination environments. Hence, the Cu^II environments are CuO₅/CuO₆/CuO₅ for the trimer and CuO₅/CuO₅ for the dimer. Each trimer and dimer has crystallographically imposed inversion symmetry. The trimer has never been observed before, the dimer has been seen only once before, and the combination of the two together in the same lattice is unprecedented. The CuO₅ cores exhibit four strong basal Cu—O bonds [1.915 (2)–1.931 (2) Å] and one weak apical Cu—O bond [2.652 (2)–2.658 (2) Å]. The CuO₆ core exhibits four strong equatorial Cu—O bonds [1.922 (2)–1.929 (2) Å] and two very weak axial Cu—O bonds [2.911 (3) Å]. The bite angles for the chelating hinokitiolate ligands range from 83.13 (11) to 83.90 (10)°.     

Structural and electrical characterisation of Li(2)O : TiO(2) : SnO(2) : P(2)O(5) electrolyte glass

Glasses of general formula 50Li(2)O : xSnO(2) : (10 -x)TiO(2) : 40P(2)O(5)(0.0 < or = x < or = 10) were investigated by differential scanning calorimetry, X-ray diffraction and ac impedance, (31)P solid-state NMR and IR spectroscopies. Three isotropic resonances can be identified in the (31)P NMR spectra, which have been assigned to various phosphate species. Analysis of the ratios of integrated intensities in the (31)P spectra leads to models for the Ti and Sn coordination environments. Both TiO(2) and SnO(2) are found to be predominantly network forming with Ti and Sn proposed to be in five- and four-coordinate environments respectively. Analysis of ac impedance spectra collected at low temperatures reveals two forms of permittivity dispersion, viz: high frequency conductivity dispersion and Cole-Cole type relaxation of permittivity. The activation energy of the relaxation frequency of the permittivity dispersion is equal to that of the dc conductivity, which is consistent with cooperative motion of lithium ions. The results also suggest that the observed increase in conductivity with temperature appears to be mainly due to an increase in mobility rather than increase in carrier concentration.     

Crystallographic report: Bis(tripyridyldiamine)zinc(II) tetrabromozincate(II) hydrate

The zinc(II) atom in the complex cation of [Zn(tpda)₂][ZnBr₄]·H₂O is octahedrally coordinated, whereas the zinc(II) atom in the anion is tetrahedrally coordinated. The cations and the anions are connected by hydrogen bonds, affording a two‐dimensional network. Copyright © 2005 John Wiley & Sons, Ltd.     

Crystallographic report: Chlorobis(pyrrolinedithiocarbamato)antimony(III)

The X‐ray crystal structure of Sb(S₂CN(CH₂)₄)₂Cl features a five‐coordinate geometry for antimony within a ClS₄ donor set, provides evidence for a stereochemical influence exerted by the lone pair of electrons on antimony, and shows no evidence for molecular aggregation. Copyright © 2003 John Wiley & Sons, Ltd.     

Luminescent (N^C^C) Gold(III) Complexes: Stabilized Gold(III) Fluorides

We report the design, synthesis, and application of a (N^C^C)‐ligand framework able to stabilize highly electron‐deprived gold(III) species. This novel platform enabled the preparation of C(sp²)‐gold(III) fluorides for the first time in monomeric, easy‐to‐handle, bench‐stable form by a Cl/F ligand‐exchange reaction. Devoid of oxidative conditions or stoichiometric use of toxic Hg salts, this method was applied to the preparation of multiple [C(sp²)‐Au^III‐F] complexes, which were used as mechanistic probes for the study of the unique properties and intrinsic reactivity of Au? F bonds. The improved photophysical properties of [(N^C^C)Au^III] complexes compared to classical pincer (C^N^C)‐Au systems paves the way for the design of new late‐transition‐metal‐based OLEDs.     

球状碳：C60及C70

本文简要介绍第三种形式的碳——C_(60)及C_(70)的发现过程、实验室制备、结构与光谱特征及形成球状Cn分子的一般原则;在最后部分,扼要提出了C_(60)的应用和研究前景。     

Crystallographic report: Bis(pyrrolinedithiocarbamato)mercury(II)

The mononuclear structure of Hg(S₂CN(CH₂)₄)₂ has crystallographically imposed twofold symmetry and features chelating dithiocarbamate ligands that form asymmetric Hg? S bond distances leading to a heavily distorted tetrahedral geometry. Copyright © 2003 John Wiley & Sons, Ltd.     

Wolfram(VI)-fluorid-pentafluorotellurate(VI): WFn(OTeF5)6-n

Tungsten(VI) Fluoride Pentafluorotellurates(VI): WF_n(OTeF₅)_6-n In WF₆ fluorine can be replaced by F₅TeO groups by means of B(OTeF₅)₃ to form WF_n(OTeF₅)_6-n. Isolation was achieved for WF₅OTeF₅ and cis-WF₄ (OTeF₅)₂. Compounds with n > 2 have been identified by ¹⁹F-nmr spectroscopy. The ligand behaviour of the F₅TeO group is compared to OMe and OPh.     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.     

Chlor(trifluorphosphan)gold(I): [Au(PF3)Cl]

Chloro(trifluorophosphane)gold(I): [Au(PF₃)Cl] X‐ray quality crystals of [Au(PF₃)Cl] (orthorhombic, Pnma) are obtained from a toluene / pentane solution at 6 °C. According to the result of the X‐ray structural analysis, [Au(PF₃)Cl] contains an almost linear F₃P‐Au‐Cl unit. The shortest Au‐Au contacts between two of these units are 3.3495(9) Å.     

meso-(2-Pyridyl)-boron(III)-subporphyrin: Perimeter Iridium(III) Coordination

Peripherally metalated porphyrinoids are promising functional π-systems displaying characteristic optical, electronic, and catalytic properties. In this work, 5-(2-pyridyl)- and 5,10,15-tri(2-pyridyl)-B^III-subporphyrins were prepared and used to produce cyclometalated subporphyrins by reactions with [Cp*IrCl₂]₂, which proceeded through an efficient C−H activation to give the corresponding mono- and tri-Ir^III complexes, respectively. While the mono-Ir^III complex was obtained as a diastereomeric mixture, a C₃-symmetric tri-Ir^III complex with the three Cp*-units all at the concave side was predominantly obtained in a high yield of 90 %, which displays weak NIR phosphorescence even at room temperature in degassed CH₂Cl₂, differently from the mono-Ir^III complexes.     

Bis(tetraethylammonium) tetrabromocobaltate(II) and bis(tetrabutylammonium) tetrabromomanganate(II): structure and magnetic properties

The crystal structures of tetrabromocobaltate(II) and tetrabromomanganate(II) salts of general formula [(C₂H₅)₄N]₂[CoBr₄] (1) and [(C₄H₉)₄N]₂[MnBr₄] (2) were determined. The manganese and cobalt cations are four-coordinated by bromide anions and they adopt a slightly distorted tetrahedral coordination. In the structure of both compounds there are neither hydrogen bonds nor any unusual short-range intermolecular interactions. Magnetic measurements of the powdered samples gave negative values of the Weiss constants equal to −4.9 and −1.1 K for (1) and (2), respectively, which suggest antiferromagnetic interactions to be transferred within the crystal lattice.     

Crystallographic report: Chlorobis(tripyridyldiamine)cadmium(II) nitrate

The Cd(II) atom in [(tpda)₂CdCl]NO₃, is octahedrally coordinated to one chlorine and five pyridyl‐nitrogen atoms. The coordination cations and nitrate anions are connected by multiple hydrogen bonds, affording a two‐dimensional structure. Copyright © 2005 John Wiley & Sons, Ltd.     

Sr(3)Co(2)O(4.33)h(0.84): an extended transition metal oxide-hydride

Reaction of the n = 2 Ruddlesden-Popper oxide Sr(3)Co(2)O(5.80) with CaH(2) yields an extended oxide-hydride phase: Sr(3)Co(2)O(4.33)H(0.84). Neutron powder diffraction data reveal the material adopts a body-centered orthorhombic structure (Immm: a = 3.7551(5) ?, b = 3.7048(4) ?, c = 21.480(3) ?) in which the hydride ions are accommodated within disordered CoO(1.16)H(0.46) layers. Low temperature neutron powder diffraction data show no evidence for long-range magnetic order, suggesting the chemical disorder in the anion lattice of the material leads to magnetic frustration.     

Crystallographic report: Bis(m‐nitrobenzoato)bis(pyridine)zinc(II)

The molecular structure of [Zn(O₂CC₆H₄NO₂‐m)₂(pyridine)₂] exhibits a distorted N₂O₂ tetrahedral geometry; the molecule has two fold symmetry. Copyright © 2005 John Wiley & Sons, Ltd.