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141.
Marek Daszkiewicz Zbigniew Staszak Adam Pietraszko Wiesława Bronowska Maria Cieślak-Golonka 《Structural chemistry》2006,17(6):599-608
Two polymeric complexes: catena(μ-CrO4-O,O′)[Co(HIm)3H2O] (1) and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO4
2− anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine
systems of varying reagent molar ratios and three excluding anions: Cl−, NO3
− and SO4
2− exclusively as mer [M(HIm)3O3]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P21
/n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and
π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution
studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution
into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the
respective d–d transition (D4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a
block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated. 相似文献
142.
Raman spectra of intramolecular vibration mode for each guest species in the methane + tetrafluoromethane (CF4) mixed-gas hydrate crystal have been measured at 291.1 K. Both of pure guest species generate the structure-I hydrate in the present pressure ranges. Isothermal phase-equilibrium curve exhibits two discontinuous points around the equilibrium methane compositions (water-free) in the gas phase of 0.3 and 0.8. At the above points, the Raman spectra of both guest molecules have been drastically changed. One of the most important findings is that the crystal of methane + tetrafluoromethane mixed-gas hydrate shows the structural phase-transition (from the structure-I to the structure-II and back to the structure-I) caused by composition changes. 相似文献
143.
Alexandra Lieb Juliane A. Kechele Robert Kraut Wolfgang Schnick Prof. Dr. 《无机化学与普通化学杂志》2007,633(1):166-171
The oxonitridoalumosilicates (so‐called sialons) MLn[Si4?xAlxOxN7?x] with M = Eu, Sr, Ba and Ln =Ho, Er, Tm, Yb were obtained by the reaction of the respective lanthanoid metal, the alkaline earth carbonates or europium carbonate, resp., AlN, “Si(NH)2” and MCl2 as a flux in a radiofrequency furnace at temperatures around 2100 °C. The compounds MLn[Si4?xAlxOxN7?x] are relevant for the investigation of substitutional effects on the materials properties due to their ability of tolerating a comparatively large phase width up to x ≈ 2.0(5). The crystal structures of the twelve compounds were refined from X‐ray single crystal data and X‐ray powder data and are found to be isotypic to the MYb[Si4N7] structure type. The compounds crystallize in space group P63mc (no. 186, hexagonal) and are made up of chains of so‐called starlike units [N[4](SiN3)4] or [N[4]((Si,Al)(O,N)3)4], respectively. These units are formed by four (Si,Al)(N/O)4 tetrahedra sharing a common central nitrogen atom. The structure refinement was performed utilizing an O/N‐distribution model according to Paulings rules, i.e. nitrogen was positioned on the four‐fold bridging site and nitrogen and oxygen were distributed equally on both of the two‐fold bridging sites, resulting in charge neutrality of the compound. The Si and Al atoms were distributed equally on their two crystallographic sites, referring to their elemental proportion in the compound, due to being poorly distinguishable by X‐ray methods. The chemical compositions of the compounds were derived from electron probe micro analyses (EPMA). 相似文献
144.
L. A. Chekulaeva I. A. Garbuzova V. V. Gavrilenko L. B. Danilevskaya V. A. Kotel'nikov 《Russian Chemical Bulletin》1996,45(9):2199-2202
Alkali metal salts of acrylamide C3H4NOM (M = Li, Na, and K) were synthesized for the first time by metallation of acrylamide with alkali metals, their alkyl derivatives, or hydrides. The structures of the compounds synthesized were studied by Raman and IR spectroscopy. Based on the results obtained, an ionic structure was proposed for the salts. The salts were tested as initiators of the anionic polymerization of acrylamide. The catalytic activity of C3H4NOM in the polymerization of acrylamide is not lower than that of the well known catalyst, KOBu1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2316–2319, September, 1996. 相似文献
145.
A. Müller E. Krickemeyer F. El-Katri D. Rehder A. Stammler H. Bgge F. Hellweg 《无机化学与普通化学杂志》1995,621(7):1160-1170
Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS3)2]2? (E = Sn, Zn, Cd), [E(CS3)3]3? (E = As, Sb, Bi, Co), {Cu(CS3)?}∞ and [Zn(CS4)2]2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh4)2[Zn(CS3)2] ( 2 ), (PPh4)2[Cd(CS3)2] ( 3 ), (PPh4)2[Sn(CS3)2] ( 4 ), (PPh4)3[As(CS3)3] ( 5 ), (PPh4)3[Sb(CS3)3] ( 6 ), (PPh4)3[Bi(CS3)3] ( 7 ), (PPh4)3[Co(CS3)3] ( 8 ) and (PPh4)Cu(CS3) ( 9 ) have been isolated. (PPh4)2[Zn(CS4)2] · CH3NO2 ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh4)2[C2S6] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, 113Cd/59Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht. 相似文献
146.
Room temperature Raman spectra of synthesized powder (FexMg1?x )2SiO4 solid solutions are obtained. Frequency trend of all modes versus composition shows clearly the existence of a step at x = 0.3. A step-like behavior of vibration frequencies at the given composition that coincides with the percolation threshold for the olivine lattice is related to the appearance of magnetic excitations in the disordered magnetic medium owing to the spin-vibration interaction. 相似文献
147.
E. U. Franck 《Journal of solution chemistry》1973,2(2-3):339-356
A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H2O and CO2–H2O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank. 相似文献
148.
The high-pressure phase transition from ambient pressure α-LiBH4 to high-pressure β-LiBH4 was observed by Raman spectroscopy and X-ray diffraction between 0.8 and 1.1 GPa. The phase boundary between these two phases was mapped over a large range of temperatures using thermal conductivity studies and differential thermal analysis. The structure of the high-pressure phase could not be identified due to small number of experimentally observed reflections, but it was shown that it is different from previously reported theoretical predictions. 相似文献
149.
The potential-dependent surface-enhanced Raman spectrum of adsorbed p-nitrobenzoic acid (PNBA) on the roughened Au electrode has been obtained by using ultraviolet (UV) excitation at 325 nm. The surface-enhanced Raman spectra of PNBA intensely changed when the voltage was in the rang of negative value, and the electrode potential at which the resonance (potential of maximum intensity) occurs varied when the vibrational mode changes, indicating that the PNBA molecules were chemisorbed on the roughened Au surface. The charge transfer (CT) mechanism could probably explain the experiment results in the present work. 相似文献
150.
From relative integrated intensity measurements of the symmetric stretching vibration of nitrate ion in nitric acid solutions (both HNO
3
/H
2
O and DNO
3
/D
2
O), the mass law concentration quotients, Q
were obtained as functions of concentration. By extrapolation the limiting dissociation constants were estimated to be 24.4 and 15 respectively at 25°C. It is shown that this constant refers to a process in which the ion pair H
3
O+ NO
3
–
is in equilibrium with the dispersed, solvated H
3
O+ and NO
3
–
ions. 相似文献