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61.
Fluorescence quenching of aromatic molecules by inorganic anions has been the subject of many investigations, yet the nature of the quenching mechanism is not fully understood. The fluorescence-quenching rate constants correlate with electrochemical data, but the radicals expected to form upon transfer of an electron to the excited aromatic molecules have escaped observation. We report the first observation of radical-ion species formed by electron-transfer quenching with inorganic anions in acetonitrile. A decisive step leading to formation of separated radical ions is the trapping of the primary charge-transfer complex by a second inorganic ion. 相似文献
62.
Flow-injection single-point titration of acids is based on biamperometric measurement of iodine formed quantitatively in the reaction of iodide with iodate. Results are presented for determination of sulphuric, hydrofluoric, monochloroacetic, formic and acetic acids. The slopes of the calibration plots, which are linear for about 1–10 rum acid, depend on the strength of the acid, decreasing from sulphuric acid to acetic acid. With microcomputer on-line data processing, relative standard deviations were about 0.2%. 相似文献
63.
Lucjan Chmielarz Piotr Kustrowski Marek Michalik Barbara Dudek Magdalena Czajka Roman Dziembaj 《Reaction Kinetics and Catalysis Letters》2007,91(2):369-378
Natural phlogophite, pre-treated with acids and intercalated with alumina pillars, was used as catalytic support. Transition
metals (Fe, Cu) were deposited on the surface of the modified clay materials by an ion-exchange method. The obtained samples
were characterized with respect to structure (XRD), texture (BET), composition (EPMA) and chemical nature of the deposited
transition metals species (UV-vis-DRS). The phlogophite based materials have been found to be active and selective catalysts
of the DeNOx process. The Fe-containing samples were catalytically active at lower temperatures than the clays modified with
copper. A competitive ammonia oxidation by oxygen decreased the effectiveness of the DeNOx process in the high temperature
range. 相似文献
64.
A simple intra- and inter-molecular potential for water molecules engaged in hydrogen bonding has been used in a one-dimensional approximation for a theoretical interpretation of the experimental correlation OH/OD versus OH in solid hydrates. The variation in the equilibrium OH(D) distance has also been considered. 相似文献
65.
Summary Complexes of 2-mercapto-1-methylimidazole (TMZ) with PtII, PdII, RhIII and RuIII of the general formulae Pt(TMZ)2Cl2, Pd(TMZ)4Cl2. Rh(TMZ)Cl3 and Ru(TMZ)Cl3 have been obtained. The thermal stabilities of the compounds were estimated by derivatographic measurements and the electron-donating atom of the measurements and the electron-donating atom of the ligand was identified from the i.r. absorbtion spectra. Lattice constants for the PtII and PdII complexes were estimated from their x-ray powder diffraction patterns. 相似文献
66.
Excitation-energy dependence of fluorescence intensity and fluorescence lifetime has been measured for 4-dimethylaminobenzonitrile (DMABN), 4-aminobenzonitrile (ABN), 4-diisopropylaminobenzonitrile (DIABN), and 1-naphthonitrile (NN) in a supersonic free jet. In all cases, the fluorescence yield decreases rather dramatically, whereas the fluorescence lifetime decreases only moderately for S1 (pi pi*, L(b)) excess vibrational energy exceeding about 1000 cm(-1). This is confirmed by comparison of the normalized fluorescence excitation spectrum with the absorption spectrum of the compound in the vapor phase. The result indicates that the strong decrease in the relative fluorescence yield at higher energies is due mostly to a decrease in the radiative decay rate of the emitting state. Comparison of the experimental results with the TDDFT potential energy curves for excited states strongly suggests that the decrease in the radiative decay rate of the aminobenzonitriles at higher energies is due to the crossing of the pi pi* singlet state by the lower-lying pi sigma*(C[triple bond]N) singlet state of very small radiative decay rate. The threshold energy for the fluorescence "break-off" is in good agreement with the computed energy barrier for the pi pi*/pi sigma* crossing. For NN, on the other hand, the observed decrease is in fluorescence yield at higher excitation energies can best be attributed to the crossing of the pi pi* singlet state by the pi sigma* triplet state. 相似文献
67.
Trávníček Zdeněk Machala Viktor Szüčová Lucie Maloň Michal Marek Jaromír 《Transition Metal Chemistry》2004,29(4):352-357
A series of new [NiX(S2P{O-c-Hex}2)(PPh3)](X = Cl–, Br–, I– and NCS–)(1)–(4) and [Ni(NCS)(S2P{OR}2)(PPh3)][R =n-Pr (5), i-Pr (6)] complexes has been synthesized and characterized by elemental analyses, f.i.r., i.r., u.v.–vis., 1H-, 13C{1H}- and 31P{1H}-n.m.r. spectra, magnetochemical and conductivity measurements. A single crystal X-ray analysis of [Ni(NCS)(S2P{O-n-Pr}2)(PPh3)](5) reveals the molecular structure of the complex and confirms a square-planar geometry around the central atom of nickel with the NCS anion coordinated via the nitrogen atom. 相似文献
68.
Erik Rakovský Ľudmila Žúrková Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):277-283
Summary. Anhydrous 1,6-hexanediammonium dihydrogendecavanadate ((HdaH2)2H2V10O28, 1) was prepared by reaction of V2O5 with 1,6-hexanediamine in aqueous solution. The crystal structure of 1 was determined, and the proton positions in the H2V10O28
4− anion were calculated by the bond length/bond number method. The protons are bound to the centrosymmetrically oriented μ–OV3 groups of the decavanadate anion. Based on the analysis of IR spectra of 1 prepared from H2O and D2O, the absorption band at 871 cm−1 can be attributed to δ(V–Ob–H) vibrations.
Received August 3, 2001. Accepted (revised) October 8, 2001 相似文献
69.
Wagner-Czauderna Elżbieta Boroń-Cegiełkowska Agata Orłowska Elżbieta Kalinowski Marek K. 《Transition Metal Chemistry》2004,29(1):61-65
The visible absorption spectra of CoCl2 in binary mixtures of acetone, dmf, dma and dmso with H2O show the existence of configuration equilibria between tetrahedral (T) and octahedral (O) species. Linear correlations between the values of log K (K = [O]/[T]) and the mole fraction of H2O,
w, have been observed in all the systems under study; their slopes decrease linearly with an increase of the donor number, DN, of the organic component of the mixture. The formation of octahedral species is enthalpy favoured but entropy disfavoured. It was found that both H and S values change linearly with
w and the slopes of these relationships depend clearly on the DN values. 相似文献
70.
Andrzejak M Sterzel M Pawlikowski MT 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(9):2029-2032
The absorption spectra of the N-(2,5-di-tert-butylphenyl) phthalimide (1-), N-(2,5-di-tert-butylphenyl)-1,8-naphthalimide (2-) and N-(2,5-di-tert-butylphenyl)-perylene-3,4-dicarboximide (3-) anion radicals are studied in terms of time dependent density functional theory (TDDFT). For these anion radicals a large number electronic states (from 30 to 60) was found in the visible and near-IR regions (5000-45,000 cm(-1)). In these regions the TD/B3LYP treatment at the 6-1+G* level is shown to reproduce satisfactorily the empirical absorption spectra of all three anion radicals studied. The most apparent discrepancies between purely electronic theory and the experiment could be found in the excitation region corresponding to D0-->D1 transitions in the 2- and 3- molecules. For these species we argue that the structures seen in the lowest energy part of the absorptions of the 2- and 3- species are very likely due to Franck-Condon (FC) activity of the totally symmetric vibrations not studied in this Letter. 相似文献