The quaternisation reaction of phosphines and amines in aliphatic alcohols. A similarity analysis using the isokinetic, isosolvent and isoselective relationships

Accurate second-order rate constants were measured at 5 K intervals in the temperature range 298.15-328.15 K for the quaternisation reaction of triethylphosphine with iodoethane in methanol, ethanol, propan-1-ol and butan-1-ol. These data are complemented previously reported rate constants for the quaternisation reaction of triethylamine with iodoethane in the same solvents and at similar temperatures. Each of these two reaction series is analysed in terms of the isokinetic relationship (IKR) with respect to solvent variation and of the isosolvent relationship (ISoR) with respect to temperature variation, using in the latter case five different empirical solvent scales. Statistically validated IKR and ISoR have been found for both reaction series. The resulting isokinetic temperatures of 347 K (phosphine series) and of 730 K (amine series) are discussed in terms of Linert's theory of the isokinetic relationship. The best ISoR correlation is obtained using the Dimroth-Reichardt E(T)(N) solvent scale for the phosphine series and the Kamlet-Taft alpha(KT) solvent scale for the amine series. It is demonstrated that no real solvent can be envisaged as having the characteristics of an isokinetic solvent. The selectivity of the nucleophiles triethylphosphine and triethylamine in the attack on iodoethane is examined by treating together both reaction series in terms of the isoselective relationship (ISeR). The isoselective temperature with respect to solvent is found to be 289 K, which is close to the value of 302 K predicted by Exner and Giese's formula on the basis of the individual isokinetic temperatures. A novel ISeR analysis with respect to temperature is performed. It reveals that the alpha(KT) scale is the most appropriate solvent scale for describing this selectivity series, and that it is feasible to find an isoselective solvent. A new equation is developed for predicting the isoselective solvent parameter from individual isosolvent parameters and is shown to yield realistic values. The present similarity analysis shows that there are significant differences between the courses of these quaternisation reactions. On the basis of the experimentally determined isoparameter values, in liquid alcohols as solvent it is proposed that the reaction between triethylphosphine and iodoethane follows a classic bimolecular nucleophilic substitution pathway, whereas the desolvation of triethylamine molecules has to be taken into account to describe the mechanism of the original Menshutkin reaction.     

Stability of Hypersurfaces with Constant r-Mean Curvature

We deal with compact hypersurfaces immersed in space forms with constant -mean curvature. They are critical points for a variational problem. We show they are stable if and only if they are geodesic spheres, generalizing results on constant curvature hypersurfaces.     

The semiclassical resolvent on conformally compact manifolds with variable curvature at infinity

We construct a semiclassical parametrix for the resolvent of the Laplacian acting on functions on nontrapping conformally compact manifolds with variable sectional curvature at infinity. We apply this parametrix to analyze the Schwartz kernel of the semiclassical resolvent and Poisson operator and to show that the semiclassical scattering matrix is a semiclassical Fourier Integral Operator of appropriate class that quantizes the scattering relation. We also obtain high energy estimates for the resolvent and show existence of resonance free strips of arbitrary height away from the imaginary axis. We then use the results of Datchev and Vasy on gluing semiclassical resolvent estimates to obtain semiclassical resolvent estimates on certain conformally compact manifolds with hyperbolic trapping.     

Preliminary evaluation of new polymer matrix for solid-phase extraction of nonylphenol from water samples

Molecularly imprinted (MIP) and blank polymers with affinity for nonylphenol were designed using computational modelling. Chromatographic tests demonstrated higher affinity of imprinted polymers towards the template nonylphenol as compared with blank polymers. The performance of both polymers in solid-phase extraction was however very similar. Both blank and imprinted polymers appeared to be suitable for the removal and pre-concentration of nonylphenol from contaminated water samples with 99% efficiency of the recovery. The commercial resins PH(EC) (Biotage) and C18 (Varian) tested in the same conditions used for comparative purposes had recovery rate <84%. The polymer capacity for nonylphenol was 231 mg g⁻¹ for blank and 228 mg g⁻¹ for MIP. The synthesised materials can have significance for sample pre-concentration and environmental analysis of this class of compounds.     

Photochemical reactions of fac-[Mn(CO)3(phen)imidazole]+: evidence for long-lived radical species intermediates

The electronic absorption spectrum of fac-[Mn(CO)(3)(phen)imH](+), fac-1 in CH(2)Cl(2) is characterized by a strong absorption band at 378 nm (epsilon(max) = 3200 mol(-1) L cm(-1)). On the basis of quantum mechanical calculations, the visible absorption band has been assigned to ligand-to-ligand charge-transfer (LLCT, im-->phen) and metal-to-ligand charge-transfer (MLCT, Mn-->phen) charge transfer transition. When fac-1 in CH(2)Cl(2) is irradiated with 350 nm continuous light, the absorption features are gradually shifted to represent those of the meridional complex mer-[Mn(CO)(3)(phen)imH](+), mer-1 (lambda(max) = 556 nm). The net photoreaction under these conditions is a photoisomerization, although, the presence of the long-lived radical species was also detected by (1)H NMR and FTIR spectroscopy. 355 nm continuous photolysis of fac-1 in CH(3)CN solution also gives the long-lived intermediate which is readily trapped by metylviologen (MV(2+)) giving rise to the formation of the one-electron reduced methyl viologen (MV(*+)). The UV-vis spectra monitored during the slow (45 min) thermal back reaction exhibited isosbestic conversion at 426 nm. On the basis of spectroscopic techniques and quantum mechanical calculations, the role of the radicals produced is analyzed.     

Different origins of green-light photoluminescence emission in structurally ordered and disordered powders of calcium molybdate

A strong greenish-light photoluminescence (PL) emission was measured at room temperature for disordered and ordered powders of CaMoO4 prepared by the polymeric precursor method. The structural evolution from disordered to ordered powders was accompanied by XRD, Raman spectroscopy, and TEM imagery. High-level quantum mechanical calculations in the density functional framework were used to interpret the formation of the structural defects of disorder powders in terms of band diagram and density of states. Complex cluster vacancies [MoO3 x V(O(z))] and [CaO7 x V(O(z))] (where V(O(z)) = V(O(X)), V(O(*)), V(O(**))) were suggested to be responsible to the appearance of new states shallow and deeply inserted in the band gap. These defects give rise to the PL in disordered powders. The natural PL emission of ordered CaMoO4 was attributed to an intrinsic slight distortion of the [MoO4] tetrahedral in the short range.     

HN2(2A') electronic manifold. II. Ab initio based double-sheeted DMBE potential energy surface via a global diabatization angle

A double-sheeted double many-body expansion potential energy surface is reported for the coupled 12A'/22A' states of HN2 by fitting about 6000 ab initio energies. All crossing seams are described to their full extent on the basis of converged results. The lowest adiabatic sheet is fitted with a rmsd of 0.8 kcal mol-1 with respect to the calculated energies up to 100 kcal mol-1 above the absolute minimum, and the topology of the first excited-state investigated with the aid of the upper adiabatic sheet. A new scheme that overcomes obstacles in previous diabatization methods for modeling global double-sheeted potential energy surfaces is also reported. The novel approach uses a global diabatization angle which allows the diabats to mimic both the crossing seams and atom-diatom dissociation limits.     

Picosecond Structural Relaxation of Abietic Acid Based Amine End Capped Para‐Phenylenevinylene Trimers in Solution

The synthesis and photophysical properties of six new abietic acid based amine end‐capped p‐phenylenevinylene trimers (AECPV3) in their lowest excited singlet states are presented. The AECPV3 compounds show a large red‐shift of both the absorption (25–30 nm) and emission (37–42 nm) maxima with respect to those of the corresponding trimers. Picosecond time‐resolved fluorescence data reveal the presence of a fast conformational relaxation process (40–62 ps) of the initially excited compounds, leading to more planar conformers. The conformational relaxation time is proportional to the volume of both the side chain and the amine groups.