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991.
Gutiérrez de Dios FJ Gómez R Feliu JM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7439-7448
Rhodium adlayers on Pt(100) substrates have been prepared by electrodeposition from dilute Rh(III) acidic solutions. The initially disordered layer is electrochemically annealed by applying a polarization program consisting of high-sweep-rate multicycle sequences between 0.05 and 0.78 V(RHE) in 0.1 M H(2)SO(4). In this way, a pseudomorphic Rh monolayer can be prepared on Pt(100) substrates. The degree of order of the electrochemically annealed layer has been evidenced not only through voltammetric experiments but also by means of scanning tunneling microscopy with atomic resolution for iodine-protected adlayers, which show a c(2 x 2) structure. The electrochemically induced ordering of the Rh adlayer appears to be a consequence of the repeated cycles of adsorption/desorption of H and, especially, oxygenated species. Voltammetry in sulfuric acid solutions permits examination of the energetics of H/anions and OH/O adsorption as a function of the Rh coverage. The first monolayer adsorbs both hydrogen and oxygenated species more strongly than the second one. This can be explained through an electronic effect caused by the underlying Pt(100) substrate. 相似文献
992.
Strong, low-energy two-photon absorption in extended amine-terminated cyano-substituted phenylenevinylene oligomers 总被引:8,自引:0,他引:8
Chung SJ Rumi M Alain V Barlow S Perry JW Marder SR 《Journal of the American Chemical Society》2005,127(31):10844-10845
Three quadrupolar oligophenylenevinylenes with five rings in the conjugated backbone, terminal donor groups, and various acceptors and/or donors along the backbone were synthesized and their two-photon spectroscopic properties investigated. These chromophores exhibit large two-photon absorption cross sections over a wide wavelength range and two distinct peaks, the strongest of which (deltamax > 3600 GM) is observed at 960-970 nm, a wavelength close to twice the value of the linear absorption maximum (2lambda(1)max). The findings on these chromophores are compared with those for analogous molecules with shorter conjugation length, for which the main two-photon band is at significantly shorter wavelength than 2lambda(1)max. 相似文献
993.
Juan Hong Liang-Fu Tang Zhi Yang Yu-Ping Zhai Mujia Nan 《Transition Metal Chemistry》2005,30(4):439-444
A series of [M(CO)5I]− and [M2(CO)10I]− anion complexes have been synthesized by the photochemical reaction of PhCH2N(CH3)3I or FcCH2N(CH3)3I (Fc=ferrocenyl) with M(CO)6 (M = Cr, Mo or W), and characterized by elemental analyses, i.r., 1H-n.m.r. and 13C-n.m.r. spectra in the case of the molybdenum and tungsten complexes. These complexes exhibit considerably different electrochemical behavior, when investigated by cyclic voltammetry. The crystal structures of [PhCH2N(CH3)3][Cr(CO)5I] and [FcCH2N(CH3)3][W2(CO)10I] have been determined by X-ray diffraction, indicating that only weak contacts maybe exist between anions and cations by the I...H bond in the former, and there are no direct interactions between anions and cations in the latter. 相似文献
994.
Vukadin M. Leovac Goran A. Bogdanović Valerija I. Češljević Ljiljana S. Jovanović Sladjana B. Novaković Ljiljana S. Vojinović-Ješić 《Structural chemistry》2007,18(1):113-119
The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H2SalGT]Cl (1), and two complexes [Cu(HSalGT)X2]·H2O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural
complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the
basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH3)3 group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions.
The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption
spectra. 相似文献
995.
Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.
Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid
Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.相似文献
996.
A binuclear complex [Cu2(DTB)(DMF)4(H2O)]·2DMF (DTB = 1,4-dinitro-2,3,5,6-tetracarboxylatobenzenic anion; DMF = N,N-dimethylformamide) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex Cu ion is located in a distorted square pyramidal environment with two oxygen atoms O(1) and O(3) from two carboxylate groups, another two oxygen atoms O(7) and O(8) from terminal ligands of two DMF molecules, and a fifth coordinated oxygen atom O(9) from the terminal ligand of one H2O molecule, in which the O(8) atom is situated in the apex of the pyramid. DTB as bridging ligand coordinates two Cu ions through its four carboxylate groups. The variable-temperature magnetic susceptibility of the complex was measured in the 5–300 K range. The magnetic coupling parameter is consistent with a ferromagnetic exchange between the two copper(II) centers and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = -2J12, 1 = 2= 1/2), giving the ferromagnetic coupling parameter of 2J = 1.80 cm- 1. This is the first example of a tetracarboxylatobenzenic bridging complex exhibiting ferromagnetic interaction. 相似文献
997.
The MnIV complex of tetra-deprotonated 1,8-bis(2-hydroxybenzamide)-3,6-diazaoctane (MnIVL) engrossed in phenolate-amido-amine coordination is reduced by HSO3− and SO32− in the pH range 3.15–7.3 displaying biphasic kinetics, the MnIIIL− being the reactive intermediate. The MnIIIL− species has been characterized by u.v.–vis. spectra {λ max, (ε, dm3 mol−1 cm−1): 285(15 570), 330 sh (7570), 469(6472), 520 sh (5665), pH=5.42}. SO42− was the major oxidation product of SIV; dithionate is also formed (18 ± 2% of [MnIV]T) which suggests that dimerisation of SO3−• is competitive with its fast oxidation by MnIV/III. The rates and activation parameters for MnIVL + HSO3− (SO32−) → MnIIIL−; MnIIIL− + HSO3− (SO32−) → MnIIL2− are reported at 28.5–45.0 °C (I=0.3 mol dm−3, 10% (v/v) MeOH + H2O). Reduction by SO32− is ca. eight times faster than by HSO3− both for MnIVL and MnIIIL−. There was no evidence of HSO3−/SO32− coordination to the Mn centre indicating an outer sphere (ET) mechanism which is further supported by an isokinetic relationship. The self exchange rate constant (k22) for the redox couple, MnIIIL−/MnIVL (1.5 × 106 dm3 mol−1 s−1 at 25 °C) is reported. 相似文献
998.
The development of microplasmas for spectrochemical analysis by optical methods is discussed. Recent achievements in miniaturization are highlighted, especially for three types of plasmas, namely high-frequency plasmas, dc-discharges and microwave plasmas. The potentials of each of these groups of plasmas as sources for atomic emission spectrometry are discussed. Literature citations and experiments indicate that the plasmas are also very useful as atom reservoirs for atomic absorption spectrometry. Methods of sampling, including feeding with gas chromatography effluents, the use of electrothermal vaporization, and the evolution of gaseous species (as shown for the case of Hg vapor), are discussed as prominent interfaces to make use of these sources for elemental analysis. 相似文献
999.
C. Dubourdieu N. Didier O. Thomas J. P. Sénateur N. Valignat Y. Rebane T. Kouznetsova A. Gaskov J. Hartmann B. Stritzker 《Analytical and bioanalytical chemistry》1997,357(8):1061-1065
Some YBa2Cu3O7-δ films and heterostructures prepared by Chemical Vapor Deposition (CVD) were analyzed in our laboratories by EPMA-EDX or WDX,
RBS, SNMS and AES. It was found that in some cases the results of composition analysis can significantly deviate from each
other. At least two main reasons for these deviations exist: the different lateral resolution and the application of different
reference samples for the calibration.
Received: 3 June 1996 / Revised: 14 October 1996 / Accepted: 16 October 1996 相似文献