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11.
Albano VG Di Serio M Monari M Orabona I Panunzi A Ruffo F 《Inorganic chemistry》2002,41(10):2672-2677
The silver-assisted ligand metathesis reaction involving a platinum(II) complex of formula [PtClMe(N,N-chelate)] with acetonitrile has been investigated. By using a suitably hindered N,N-chelate, an otherwise hardly detectable trinuclear species has been isolated and characterized through X-ray diffractometry. The trinuclear cation consists of two nearly orthogonal [PtCl(Me)(N,N-chelate)] square-planar units entrapping an Ag(+) cation through the chloride ligands that, acting as bidentate, form a linear AgCl(2) unit with two nonequivalent Ag-Cl bonds. The residual acidity of the silver cation is satisfied by one secondary Ag-Pt interaction [Ag-Pt(1) = 2.82 A] in which the platinum atom acts as a donor. Kinetic studies have demonstrated that the silver assistance operates both through a simple associative step and through a pathway in which the above trinuclear complex is an active intermediate. In a noncoordinating solvent the latter species evolves with AgCl loss and formation of a dinuclear Pt,Pt complex showing a rare single chloride bridge. 相似文献
12.
13.
Melucci M Barbarella G Gazzano M Cavallini M Biscarini F Bongini A Piccinelli F Monari M Bandini M Umani-Ronchi A Biscarini P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(28):7305-7312
A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior. 相似文献
14.
15.
In real catalyst systems, it is difficult to establish a correlation between catalytic properties and the shape (crystal planes, corners and steps) of the active catalytic particles. In this paper we present a clear shape dependence of the catalytic properties of a Vulcan‐supported fuel cell catalyst having 4 nm cubo‐octahedral platinum(0) nanocrystallites with (111) and (100) surfaces stabilized by sodium polyacrylate. The electrode materials were characterized by CO‐stripping cyclic voltammetry and transmission electron microscopy (TEM), showing that no agglomeration had occurred among the nanoparticles on the catalyst surfaces. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
16.
A. Paolone P. Roy A. Pimenov A. Loidl A.A. Mukhin A.M. Balbashov 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,16(2):245-250
The optical conductivity of La0.85Sr0.15MnO3 single crystals was studied by means of submillimeter and infrared spectroscopy for frequencies cm-1 and temperatures 10 K <
T
<300 K. The submillimeter conductivity follows the temperature dependence of the dc-data. The phonon spectrum of La0.85Sr0.15MnO3 changes considerably below K revealing a structural phase transition induced by charge or orbital order. At T
=10 K a number of phonon modes can be identified in addition to the room-temperature spectrum. The optical conductivity () in the mid-infrared reveals the characteristics of small polaron absorption. Below the magnetic ordering temperature the
polaron binding energy is highly reduced, but the onset of charge order interrupts the formation of free charge carriers with
a Drude-like behavior. The frequency and temperature dependence of in this regime qualitatively resembles the small polaron predictions by Millis et al. (Phys. Rev. B 54, 5405 (1996)).
Received 5 November 1999 相似文献
17.
Giovanni Ghigo Matteo Bonomo Achille Antenucci Chiara Reviglio Stefano Dughera 《Molecules (Basel, Switzerland)》2022,27(6)
Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism. 相似文献
18.
The classical Lindstedt–Poincaré method is adapted to analyze the nonlinear normal modes of a piecewise linear system. A simple
two degrees-of-freedom, representing a beam with a breathing crack is considered. The fundamental branches of the two modes
and their stability are drawn by varying the severity of the crack, i.e., the level of nonlinearity. Results furnished by
the asymptotic method give insight into the mechanical behavior of the system and agree well with numerical results; the existence
of superabundant modes is proven. The unstable regions and the bifurcated branches are followed by a numerical procedure based
on the Poincarè map. 相似文献
19.
The stability of a cantilever elastic beam with rectangular cross-section under the action of a follower tangential force and a bending conservative couple at the free end is analyzed. The beam is herein modeled as a non-linear Cosserat rod model. Non-linear, partial integro-differential equations of motion are derived expanded up to cubic terms in the transversal displacement and torsional angle of the beam. The linear stability of the trivial equilibrium is studied, revealing the existence of buckling, flutter and double-zero critical points. Interaction between conservative and non-conservative loads with respect to the stability problem is discussed. The critical spectral properties are derived and the corresponding critical eigenspace is evaluated. 相似文献