The comparative interfacial oxidation kinetics of the approximate structural isomers trans-(O)2ReV(py)+4 and cis-(O)2ReV(bpy)(py)+2 (py, pyridine; bpy, 2,2′-bipyridine) have been assessed in aqueous solution via conventional cyclic voltammetry at a highly ordered pyrolytic graphite (HOPG) electrode. HOPG was employed because of its known propensity to diminish interfacial electron transfer (ET) rates (by ca. three to four orders of magnitude) and because of a probable lack of importance of kinetic work terms (diffuse double-layer corrections). Measured rates for the trans complex exceed those for the cis by about a factor of 3. Expressed as an effective activation Gibbs energy difference ΔG*, this corresponds to a cis-trans difference of ca. 3 kJ mol−1. The actual vibrational barriers to ET have determined from a combination of published X-ray structural results (trans complex) and new resonance Raman results (cis complex). The values are 0.6 kJ mol −1 for the trans oxidation and 4.4 kJ mol−1 for the cis oxidation (i.e. close to the barrier difference inferred from rate measurements). Further analysis shows that most of the barrier difference is associated with displacement of a (predominantly) Re-N(bpy) stretching mode found only in the cis system. Differences in metal-oxo displacements (cis > trans) are also implicated. 相似文献
Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis{3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N′-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13–0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 108–109 s−1, independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis. 相似文献
The rate of electron transfer from organic sulfides to [CrV(ehba)2]− (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO4−, HSO5− and HCO4− oxidation of organic sulfides. 相似文献
The reactive ion etching of GaAs, InP, InGaAs, and InAlAs in CF3Br/Ar discharges was investigated as a function of both plasma power density (0.56-1.3 W - cm–2) and total pressure (10-40 mTorr) The etch rate of GaAs in 19CF3Br:1Ar discharges at 10 m Torr increases linearly with power density, from 600 Å min–1 at 0.56 W · cm–2, to 1550 Å · min at 1.3 W · cm–2. The in-based materials show linear increases in etch rates only for power densities above – 1.0 W · cm–2. These etch rates are comparable to those obtained with CCI2F2:O2 mixtures under the same conditions. Smooth surface morphologies and vertical sidewalls are obtained over a wide range of plasma parameters. Reductions in the near-surface carrier concentration in n-type GaAs are evident for etching with power densities of >0.8 W cm–2, due to the introduction of deep level trapping centers. At 1.3 W· cm–2, the Schottky barrier height of TiPtAu contacts on GaAs is reduced from 0.74 to 0.53 eV as a result of this damage, and the photoluminescent intensity from the material is degraded. Alter RIE, we detect the presence of both F and Br on the surface of all of the semiconductors. This contamination is worse than with CCl2F2-based mixtures. High-power etching with CF3Br/Ar together with Al-containing electrodes can lead to the presence of a substantial layer of aluminum oxide on the samples if the moisture content in the reactor is appreciable. 相似文献
Changes of the rheological properties of hyaluronic acid (sodium-magnesium salt) solutions after exposure to UV radiation
indicate a vigorous decrease in their viscosity, but its still strong shear rate dependence. Whereas the presence of the singlet
oxygen sensitizer (anthracene-1-sulphonic acid) brings about a loss of shear dependence; the studied solutions show newtonian
behavior. 相似文献
fine structure was observed in the conductance curve of a tunneling junction composed of a single crystalline Bi2212 and an evaporated SnO2 film. It is similar to those of Bi2212-GaAs mechanical junctions and there is a certain correspondence between the structure and the phonon density of states. Thus the previous conclusion that the structure is due to phonons has been complemented by this work. The energy gap 2 was 57 meV at 13 K and Tc was 78 K. 2(0)/kBTc is then 8.3. (T) showed the BCS-like temperature dependence. 相似文献
Preparation, Raman Spectra, and Crystal Structures of V2O3(SO4)2, K[VO(SO4)2], and NH4[VO(SO4)2] The oxo-sulfato-vanadates(V) V2O3(SO4)2, K[VO(SO4)2], and NH4[VO(SO4)2] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V2O3(SO4)2 consists of a threedimensional network of pairs of cornershared VO6 octahedra with one terminal oxygen atom each, and SO4 tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH4[VO(SO4)2] and K[VO(SO4)2] are isostructural. VO6 octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO3 molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO4)2] ? K[VO2(SO4)] + SO3 at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V2O3(SO4)2, monoclinic, space group P21/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(Rw) = 0.039(0,033); K[VO(SO4)2], orthorhombic, space group P212121, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(Rw) = 0,11(0,10); NH4[VO(SO4)2], orthorhombic, space group P212121, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(Rw) = 0.088(0.083). 相似文献
The photochemistry of some members of the two series of γ-phenyl substituted acyclic β, γ-unsaturated ketones 1 and 2 upon direct irradiation with γ 310nm has been investigated, viz 1c–1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c–1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde. The β-phenyl β, γ-UK 3a proved to be photostable. The 1,3-acyl shift products of 1c–1h result mainly from the singlet excited state in a cage radical process. The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical. It is proposed that the formation of the (Z)-isomer proceeds from 1T(π -π*) which is populated according to . Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively. 相似文献
Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds tC4H9N?VCp(NHtC4H9)[P(SiMe3)2] and tC4H9N?VCp(NiProp2)(PR2) (R?SiMe3, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF2)2V2Cl2)(NtC4H9)2]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [tC4H9N?VCl2 · PPh3]+PF6? has been isolated. 1 reacts with an excess of diisopropylamine forming tC4H9N?V(NiProp2)Cl2 ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds tC4H9N?VCp(NiProp2)Cl ( 3 ) and tC4H9N?V(NiProp2)X2 (X?CH2CMe3, OtC4H9, CH3COO) has been prepared. All compounds obtained are characterized by 1H, 51V, 31P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom. 相似文献