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61.
Ion Pairing in Protic Ionic Liquids Probed by Far‐Infrared Spectroscopy: Effects of Solvent Polarity and Temperature 下载免费PDF全文
Dr. Koichi Fumino Verlaine Fossog Peter Stange Kai Wittler Wigbert Polet Prof. Dr. Rolf Hempelmann Prof. Dr. Ralf Ludwig 《Chemphyschem》2014,15(12):2604-2609
The cation–anion and cation–solvent interactions in solutions of the protic ionic liquid (PIL) [Et3NH][I] dissolved in solvents of different polarities are studied by means of far infrared vibrational (FIR) spectroscopy and density functional theory (DFT) calculations. The dissociation of contact ion pairs (CIPs) and the resulting formation of solvent‐separated ion pairs (SIPs) can be observed and analyzed as a function of solvent concentration, solvent polarity, and temperature. In apolar environments, the CIPs dominate for all solvent concentrations and temperatures. At high concentrations of polar solvents, SIPs are favored over CIPs. For these PIL/solvent mixtures, CIPs are reformed by increasing the temperature due to the reduced polarity of the solvent. Overall, this approach provides equilibrium constants, free energies, enthalpies, and entropies for ion‐pair formation in trialkylammonium‐containing PILs. These results have important implications for the understanding of solvation chemistry and the reactivity of ionic liquids. 相似文献
62.
Stephan Ludwig Dr. Kai Helmdach Mareike Hüttenschmidt Elisabeth Oberem Dr. Jabor Rabeah Dr. Alexander Villinger Prof. Dr. Ralf Ludwig Prof. Dr. Wolfram W. Seidel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16811-16817
A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)(PPh3)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)-(PPh3)], in which valence trapped WIII/RuII and WII/RuIII cationic species are at equilibrium. 相似文献
63.
C12H10N2O2; monoclinic, space group P1 21/c 1 (Z = 2), 826 observed independent reflexions, R = 0.043; lattice dimensions at 25 °C, a = 975.8(3) pm, b = 466.8(1) pm, c = 1186.8(2) pm, β = 108.51(1)°. 相似文献
64.
H. Seliger M. Eppel E. Gldner I. Kittel A. Ludwig R. Schorr 《Macromolecular Symposia》1992,58(1):215-220
Oligomers of defined sequence and structure modelling main chain LC polymers were prepared a) by solution synthesis; b) by a novel liquid phase synthesis using two monomethoxy-poly (ethylene glycol) supports. Benzyl- and tert.butyl-groups were used as orthogonal pair of protecting groups for route a), and also as compatible anchor groups for carriers in route b). Depending on chain structure and end groups, at least ca. 3 mesogenic elements are required to allow for LC phase transitions. The phase behaviour of oligomers with free carboxylic ends can be explained by their association tendency. 相似文献
65.
Subramaniam AR Gruzberg IA Ludwig AW Evers F Mildenberger A Mirlin AD 《Physical review letters》2006,96(12):126802
We develop the concept of surface multifractality for localization-delocalization (LD) transitions in disordered electronic systems. We point out that the critical behavior of various observables related to wave functions near a boundary at a LD transition is different from that in the bulk. We illustrate this point with a calculation of boundary critical and multifractal behavior at the 2D spin quantum Hall transition and in a 2D metal at scales below the localization length. 相似文献
66.
M. Ludwig P. Abell 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,58(1):97-105
Social networks in communities, markets, and societies self-organise through the interactions of many individuals. In this
paper we use a well-known
mechanism of social interactions — the balance of sentiment in triadic
relations — to describe the development of social networks. Our model
contrasts with many existing network models, in that people not only
establish but also break up relations whilst the network evolves. The
procedure generates several interesting network features such as a variety
of degree distributions and degree correlations. The resulting network
converges under certain conditions to a steady critical state where temporal
disruptions in triangles follow a power-law distribution. 相似文献
67.
Prof. Dr. Ludwig Reich 《Monatshefte für Mathematik》1975,79(2):139-145
The well known theorem of H. Poincaré concerning the analytic continuation and representation along a curve of solutions of differential equations depending on a parameter is generalized to solutions of Differential Equations of Briot-Bouquet type depending on a parameter.
Herrn Professor Dr. N. Hofreiter zum 70. Geburtstag 相似文献
Herrn Professor Dr. N. Hofreiter zum 70. Geburtstag 相似文献
68.
Ludwig Arnold 《Linear algebra and its applications》1976,13(3):185-199
It is proved that Wigner's semicircle law for the distribution of eigenvalues of random matrices, which is important in the statistical theory of energy levels of heavy nuclei, possesses the following completely deterministic version. Let An=(aij), 1?i, ?n, be the nth section of an infinite Hermitian matrix, {λ(n)}1?k?n its eigenvalues, and {uk(n)}1?k?n the corresponding (orthonormalized column) eigenvectors. Let , put (bookeeping function for the length of the projections of the new row v1n of An onto the eigenvectors of the preceding matrix An?1), and let finally (empirical distribution function of the eigenvalues of . Suppose (i) , (ii) limnXn(t)=Ct(0<C<∞,0?t?1). Then ,where W is absolutely continuous with (semicircle) density 相似文献
69.
The magnetic properties of annealed Fe-Pt multilayer thin films with a broad composition range were investigated in order to identify the effects of composition and annealing temperature on the achievable coercive field, and to identify its maximum at low processing temperatures. Two types of multilayer systems were deposited as materials libraries to vary the composition from Fe20Pt80 to Fe75Pt25. The first type of multilayer was comprised of alternating opposing wedges, whereas the second type consisted of repeated uniform Fe and Pt layers interspersed periodically with Fe wedge layers. It was found that coercive fields μ0HC > 0.7 T can be achieved at an annealing temperature of about 300 °C (60 min) for both types of multilayers as long as the composition is close to 50:50. Higher annealing temperatures are needed for films, which deviate from this composition. Increasing the annealing temperature up to 700 °C leads to increased coercivity values. Multilayers with additional Fe layers showed increased remanence but reduced coercive fields. 相似文献
70.
Dr. Christoph Ludwig Teske Dr. Anna-Lena Hansen Prof. Dr. Richard Weihrich Prof. Dr. Lorenz Kienle Marius Kamp Kasper Pieter van der Zwan Prof. Dr. Jürgen Senker Dr. Carsten Dosche Prof. Dr. Gunther Wittstock Prof. Dr. Wolfgang Bensch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6763-6772
A new preparation route is developed for the synthesis of needle-like crystals of [Au(S2CNH2)2]SCN, which avoids disproportionation of the AuI salt used as a starting material. In the crystal structure, the two crystallographically independent AuIII centers are in a square-planar environment of two S2CNH2 ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules. Density functional theory (DFT) calculations including dispersion and damping corrections result in a unit cell volume very close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 μm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composed of nanosized crystals with a volume-weighted average domain size of 20(1) nm. According to results of X-ray photoemission experiments, the black needles are covered by a nitrogen-rich carbon nitride with composition near (CN)2N. 13C solid-state NMR investigations indicate that two different carbon species are present, with signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidences that the needles are composed of slightly elongated nanoparticles. 相似文献