Construction of a Novel 2D Polymer [Co（dmpzm）（dca）2]∞ from Reaction of a Mononuclear Complex [Co（dmpzm）Cl2] with Sodium Dicyanamide （dca） [dmpzm=bis（3,5-dimethylpyrazolyl）methane]

Reaction of COC12.6H20 with equimolar bis（3,5-dimethylpyrazolyl）methane （dmpzm） produced a mononuclear adduct [Co（dmpzm）Cl2] （1）. Treatment of 1 with sodium dicyanamide （dca） afforded a polymeric complex [Co（dmpzm）（μ-dca）2]∞ （2）. 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network （extended along the bc plane） in which the { [Co（dmpzm）（μ-dca）]2} n^2n＋ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated.     

Nuclear magnetic resonance spectroscopic study on ionic liquids of 1-alkyl-3-methylimidazolium salts

Chemical shifts of ¹H and ¹³C NMR of series of methylimidazolium salts (MIM⁺, X=Br⁻, BF₄⁻ and PF₆⁻) function on the length of alkyl groups on the ring, type of solvents and the concentration. The bromides series demonstrate more chemical shift variation on H2 upon the change of solvents and concentration. Unexpected H-D exchange reactions were also observed in the MIM⁺Br⁻ by using CD₃OD and D₂O. The exchange rates strongly depend on the length of the alkyl group, which could cause more steric factor to reduce the interaction between deuterium atom from solvent and C2 of the ring.     

Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Magnetic microcapsules for targeted delivery of anticancer drugs

To achieve targeted distribution of anticancer drugs with sustained activity, ferromagnetic ethylcellulose microcapsules containing an anticancer drug, mitomycin C (FM-MMC-mc), were prepared by a method based on phase separation principles. Two prototypes of FM-MMC-mc were made: one with the drug as the core and zinc ferrite on its capsular surface (outer type); the other with both the drug and zinc ferrite as the core (inner type). Both preparations provided a sustained-release property and a sensitive response to conventional magnetic force, although certain differences in the release rate of drug, magnetic responsiveness, and particle size were found between the two dosage forms. Animal studies showed that the magnetic microcapsules could be magnetically controlled in the artery and urinary bladder. VX2 tumors in the rabbit hind limb and urinary bladder were successfully treated with magnetic control of FM-MMC-mc. Pharmacokinetic study revealed that the targeting of the microcapsules markedly enhanced the drug absorption into the surrounding tissues for a prolonged period of time. The results indicate the feasibility and effectiveness of the magnetic microcapsules as a targeted drug delivery system.     

Flow through Porous Media XVI: Electrokinetic Transport Coefficients of Aqueous Solutions of Mercuric Chloride and Glycine through a Sintered Disc Impregnated with a Cellulose Acetate Membrane under a Magnetic Field

The effect of the magnetic field on the electrokinetic transport coefficients (permeability coefficient and electro-osmotic permeability coefficient) of water and aqueous solutions of mercuric chloride and glycine through a sintered disc impregnated with cellulose acetate at different potentials, concentrations, and magnetic fields varying up to 21 kg/cm² are reported at 308.15 K. The phenomenological coefficients characterizing the electro-osmotic flow and the membrane characteristics are also estimated for the various solutions with the object of determining the efficiencies of electrokinetic energy conversion and ζ potential. The effect of magnetic field has been attributed to the molecular orientation of dipoles in solutions and to the change in the structure of the membrane.     

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Inorganic Metal Complexes. Conducting Salts of Bis(ethylenediseleno)tetrathiafulvalene (BEST) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside

The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN)₆]³⁻ or the photochromic nitroprusside anion [Fe(CN)₅NO]²⁻ are reported: (BEST)₄[Fe(CN)₆] (1), (BEST)₃[Fe(CN)₆]₂·H₂O (2) and (BEST)₂[Fe(CN)₅NO] (3). Salts 1 and 3 show a layered structure with alternating organic (β-type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST)²⁺ dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity and a semiconducting-semiconducting transition at ca. 150 K which has been attributed to a dimerization in the organic sublattice.     

Topologisch und elektronisch bemerkenswerte „reduzierte”︁ Cluster des Typs [V18O42(X)]n− (X = SO4, VO4) mit Td-Symmetrie und davon abgeleitete Cluster [V(18–p)As2pO42(X)]m− (X = SO3, SO4, H2O; p = 3, 4)

Reduced Clusters with Remarkable Topological and Electronic Properties of the Type of [V₁₈O₄₂(X)]^n? (X = SO₄, VO₄) with T_d-Symmetry and Related Clusters [V_(18—p)As_2pO₄₂(X)]^m? (X = SO₃, SO₄, H₂O; p = 3, 4) The novel cluster-compounds Na₆[V₁₈O₄₂H₉(VO₄)] · 21 H₂O, (NH₄)₈[V₁₈O₄₂(SO₄)] · 25 H₂O, K₆[V₁₅As₆O₄₂(H₂O)] · 8 H₂O, (NH₄)₆[V₁₄As₈O₄₂(SO₃)], (NH₄)₆[V₁₄As₈O₄₂(SO₄)] and [N(CH3)₃]₄[₄V₁₄As₈0₄₂(H₂0)] were prepared and characterized by IR- and UV/Vis/NIR-spectroscopy, magnetic measurements and complete crystal structure analysis. For structural data see Inhaltsübersicht. Topological relations to the rhombicuboctahedron spanned by 24 0-atoms of the genuine hypothetical a-Keggin ion, at which the square planes are capped by V?O or As₂O groups, are discussed. Of particular interest are the ?extended”? Keggin ions [V₁₈O₄₂(X)]ⁿ- (X = SO₄ VO₄), (formaly derived from the hypothetical genuine a-Keggin ion by addition of six V?O groups) which have quite different electron populations in spite of the same structure of their cluster shells.     

Über Chalkogenolate. 206 [1]. N-Thioacetyldithiocarbamate und Ester der N-Thioacetyldithiocarbamidsäure

On Chalcogenolates. 206. N-Thioacetyl Dithiocarbamates and Esters of N-Thioacetyl Dithiocarbamic Acid Thioacetamide reacts with carbon disulfide in the presence of KH to form via the tetrabutyl ammonium salt dark yellow N-thioacetyl dithiocarbamates M[S₂C? NH? CS? CH₃], where M = K, Rb, Cs. The salts as well as the methyl and ethyl ester have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Attempts to synthesize N-thioacetyl dithiocarbamic acid were not successful.     

聚合物{[CuII(Hpb) (mal)]H2O}n :单体的量子化学计算和磁性研究

{[Cu^Ⅱ（Hpb）（mal）]H=O}n （Hpb=2-2＇-pyridylbenzimidazole, mal=maleic acid） is a helical chain-like polymer complex. In order to investigate the electronic structure of the complex, the monomer Cu^Ⅱ（Hpb）（mal） was obturated with different functional groups respectively. For these selective segments, the geometry optimizations were conducted by using hybrid DFT （B3LYP）methods to find that the structure obturated with H2O was better consistent with the experiment, and then this model would be used to latter calculations, such as the frontier molecular orbital and the NBO charge population analysis. In addition the magnetic behaviors of this complex were analyzed by experiments and the weak antiferromagnetic couple between copper（Ⅱ） ions was observed. The exchange coupling constant was calculated by DFT based on the spin broken symmetry formalism. The calculated coupling constants were in good agreement with the experimental data.